CN101830805A - Fluoropyrethroid containing compound as well as synthesis method and application thereof - Google Patents
Fluoropyrethroid containing compound as well as synthesis method and application thereof Download PDFInfo
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- CN101830805A CN101830805A CN 201010172052 CN201010172052A CN101830805A CN 101830805 A CN101830805 A CN 101830805A CN 201010172052 CN201010172052 CN 201010172052 CN 201010172052 A CN201010172052 A CN 201010172052A CN 101830805 A CN101830805 A CN 101830805A
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Abstract
The invention discloses a fluoropyrethroid containing compound as well as a synthesis method and application thereof, belonging to the technical field of organic insect disinfestation. The compound has the structure general formula (I) shown in the specification,; and in the general formula (I), R represents a part of alcoholic compound of the traditional pyrethroid and also comprises mixture of various stereoisomer forms and various spatial configuration compounds of the compound. The invention also relates to a method for producing the ester type compound (I) containing the fluoropyrethroid compound (I) active ingredient as one effective medicine for controlling harmful insects. The invention discloses the application of the compound and an insecticidal mixture containing the compound as the active ingredient in the aspect of controlling the harmful insects.
Description
Technical field
The present invention relates to a kind of fluorine-containing pyrethroid compound, its synthetic method and purposes belong to organic desinsection class pyrethroid technical field.
Background technology
Pyrethroid is lipophilic organic compound, wherein pyrethrin all obtains from pyrethrum is spent, they have shown very strong insecticidal activity, and just being based on the sodium-ion channel effect that influences on the insect neural film on one's body just has so powerful insecticidal activity.
R wherein
1, R
2Can be-H-CF
3Or-CH
3(EPA0638543, EPA0779269 etc.) this compounds all is used as sterilant, and has shown excellent insecticidal activity, yet along with using dosage increases, has also shown such as effect, the scope of dosage, control insect pest, the uncomfortable problem of toxicity or the like.Therefore we must constantly research and develop the new sterilant after modifying improvement on the agent structure.
Summary of the invention
The objective of the invention is to:
1. synthetic a kind of fluorine-containing pyrethroid compound, and this compounds screened, filter out sanitary insect pests such as mosquito, fly, cockroaches, agricultural pests such as aphid, blue or green worm all has the high ability of knocking down, kill capability and stifling, stomach toxicity, action of contace poison, has some compounds of the insecticidal active ingredient of efficient, low toxicity and low residue.
2. the synthesis preparation method of above-mentioned these compounds of screening is provided.
3. the monomer of the above-mentioned compound that filters out or mixture and preparation thereof are applied in domestic hygiene medication and agricultural chemicals aspect.
Very lucky, we find as a kind of compound (I) of new general formula has very excellent pesticidal effect in this respect.
The objective of the invention is to be achieved through the following technical solutions:
A kind of fluorine-containing pyrethroid compound that provides with general formula (I):
The R part that provides in the mutual-through type of the present invention (I) employed alcohol moiety from existing pyrethroid has carried out optimizing screening, optimization has higher saturated vapor pressure, under normal temperature and high temperature, still can stablize and continue volatilization, good drug efficacy, 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.
Wherein the wide range of R comprises the alkane that contains 1～18 carbon atom; Contain the benzene alkane that can be replaced by one or more substituted radicals, substituted radical comprises the alkane of 1～4 carbon atom, 2～6 haloolefin, the halo alkynes of 2～6 carbon atoms, the diolefine of 4～8 carbon atoms or halogen.
R also comprise other functional groups as:
Wherein replace the R of group
1For-H ,-CH
3R
2For: monocyclic aromatic hydrocarbons or-CH
2-C ≡ CH;
Or be
Wherein B representative-O-or-S-,-C (O)-or-CH
2-, R
2Expression-H ,-CH
3,-CONH
2,-CSNH
2, or-C ≡ CH, R
3Represent halogen atom, or-CH
3, on behalf of numeral, n equal 0,1, and perhaps 2;
Or be
R4 wherein, R5, R6, R7 can represent-H ,-Cl ,-CH
3
Also have group:
R wherein
8Represent hydrogen atom or-C ≡ CH or-CN, R
9, R
10, R
11, R
12, R
13Representative-H, halogen atom, alkyl comprises the oxoalkyl group or the alkylthio of eight carbon atoms, and is saturated or undersaturated, or arbitrarily by one or more-H ,-CN ,-NO
2,-NH
2Perhaps-group of OH.
R wherein
14And R
15Representative-CH respectively
3,-CH
2F ,-CHF
2Perhaps-CF
3Group.
The R that studies screening through the inventor is (a) 1-ethynyl-2-methylpent-2-thiazolinyl; (b) 2,5-dioxy-3-(2-propynyl)-1-imidazolidyl methyl; (c) 2,3,5,6-tetrafluoro-4-methyl-benzyl; (d) 2,3,5,6-tetrafluoro-4-methoxy-benzyl; (e) 2,3,5, the 6-ptfe benzyl; (f) 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl; (g) 2-methyl-3 phenylbenzyl.
When R is (a) 1-ethynyl-2-methylpent-2-thiazolinyl, compound (X1) is 1-ethynyl-2-methylpent-2-thiazolinyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (b) 2,5-dioxy-3-(2-propynyl)-1-imidazolidyl methyl, compound (X2) are [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (c) 2,3,5,6-tetrafluoro-4-methyl-benzyl, compound (X3) is 2,3,5,6-tetrafluoro-4-methyl-benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (d) 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl, compound (X4) is 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (e) 2,3,5, the 6-ptfe benzyl, compound (X5) is 2,3,5,6-ptfe benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (f) 3-phenoxy benzyl, compound (X6) is 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester
When R is (g) 2-methyl-3-phenylbenzyl, compound (X7) is 2-methyl-3-phenylbenzyl-3-(2-fluoro-1-propenyl)-2,2 dimethyl cyclopropane carboxylic acid's esters.
The invention provides a kind of 3-of containing (2-fluoro-1-propenyl)-2, the desinsection of 2-dimethyl cyclopropane carboxylic acid ester mixture (sterilant).This compound general formula (I) accounts for lower ratio at pesticide active ingredient, has guaranteed the effective insecticidal effect when having reduced the sterilant consumption.
Described a kind of fluorine-containing pyrethroid compound, it is characterized in that cyclopropane 1 in the The compounds of this invention general formula (I), 3 chiral carbon atoms have optical isomer, and levo form S-body and dextrorotatory form R-body also exist geometrical isomer Trans, Cis, Z and E on the cyclopropane ring and on the carbon-carbon double bond; The compounds of this invention comprises that all have the active optical isomer of pest control, geometrical isomer and composition thereof.
The embodiment of mixture of the present invention comprises, for example, and following compound:
A kind of fluorine-containing pyrethroid compound shown in the compound structure general formula (I), wherein 1 absolute configuration is a S-body configuration on the cyclopropane ring; It is the left-handed rotation type;
A kind of fluorine-containing pyrethroid compound shown in the compound structure general formula (I), wherein on the cyclopropane ring on 1 bit substituent and the cyclopropane ring relative configuration of 3 bit substituents are transconfigurations, i.e. trans configuration;
A kind of fluorine-containing pyrethroid compound shown in the compound structure general formula (I), wherein 1 absolute configuration is a S-body configuration on the cyclopropane ring, be the left-handed rotation type, on the cyclopropane ring on 1 bit substituent and the cyclopropane ring relative configuration of 3 bit substituents are transconfigurations, i.e. trans configuration;
A kind of fluorine-containing pyrethroid compound shown in the compound structure general formula (I), wherein 1 absolute configuration is a S-body configuration on the cyclopropane ring, be the left-handed rotation type, on the cyclopropane ring on 1 bit substituent and the cyclopropane ring relative configuration of 3 bit substituents are transconfigurations, i.e. trans configuration; Be configured as cis-configuration, i.e. Z configuration on two keys;
A kind of fluorine-containing pyrethroid compound shown in the compound structure general formula (I) wherein comprises 51% or more isomer, and 3 absolute configuration is the R-body on its cyclopropane, i.e. right-handed rotation type;
A kind of fluorine-containing pyrethroid compound shown in the compound structure general formula (I) wherein comprises 51% or more isomer, on its cyclopropane ring on 1 bit substituent and the cyclopropane ring relative configuration of 3 bit substituents be transconfiguration, i.e. trans configuration;
A kind of fluorine-containing pyrethroid compound shown in the compound structure general formula (I), wherein comprise 51% or more isomer, 3 absolute configuration is the R-body on its cyclopropane, it is the right-handed rotation type, on the cyclopropane ring on 1 bit substituent and the cyclopropane ring relative configuration of 3 bit substituents be transconfiguration, i.e. trans configuration.
The present invention also provides the synthesis technique of above-mentioned a kind of fluorine-containing pyrethroid compound, and this synthesis technique is as follows:
With general formula (A) expression acyl chlorides
With general formula (B) expression carboxylic acid
With general formula (C) expression alcohol
HO-R(C)
Wherein R is by the group of formula (a) and (b), (c), (d), (e), (f), (g) expression.
General formula (A) or general formula (B) just can obtain The compounds of this invention general structure (I) series compound with the alcohol of general formula (C) expression by esterification.
The compounds of this invention general structure (I) pyrethroid compound carries out structural identification through infrared spectrometer (IR), gas chromatography instrument (GC/MS) and three kinds of structural analysis instruments of nuclear magnetic resonance spectrometer (NMR).
Above-mentioned single stage method of the present invention can satisfy the requirement of invention quality product, 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, the product yield height, purity can reach more than 95%, and therefore, above-mentioned synthesis technique is a kind of operational path and the preparation method with wide prospects for commercial application in this area.
The compounds of this invention is a kind of insect is had fabulous preventive and therapeutic effect and has 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, stable to light, the activity of pyrethroid there is the compound of enhancement structural safety, people and animals is stimulated little.
Monomer, mixture that the present invention will have active each compound are mixed with various formulation sterilants and are applied to domestic hygiene medication and agriculture medication aspect.
The medication that above-mentioned various formulation sterilant is applied to domestic hygiene is meant the preparation of the household insect that is used to prevent and treat mosquito, fly, Groton bug, ant or louse aspect, as the disc type insecticidal incense, and electric mosquito repellent tablet, vaporizer mosquito liquid or the agent of desinsection gas evil.
Above-mentioned various formulation sterilant is used the pharmaceutical preparation that agriculture medicament is meant multidisciplinary insects such as bollworm twill in control fruit tree, the vegetables cash crop vegetation, noctuid, cabbage caterpillar, aphid.
Below to the compound general formula (I) of structure of the present invention for activeconstituents is prepared into mixture, this mixture 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.
Insecticidal compositions of the present invention comprises The compounds of this invention and inert support, and it is prepared with universal method.
Above-mentioned will have active each compound monomer, mixture to be mixed with various formulation sterilants be missible oil, emulsifiable concentrate, wettable powder, mobile preparation (as water emulsion), pulvis, granule, aerosol, heating volatile preparation (as mosquito-repellent incense, electric mosquito repellent tablet, vaporizer mosquito liquid), non-heating volatile preparation, heating fumigating agent (as flammable fumigant, chemical fumigant, the unglazed porcelain fumigant of porous), smoke-like preparation (as fumicants, aerosol), ultra-low volume (ULV) preparation and poison baits such as volatilization, fan volatilization naturally.
For example, compound method is as mentioned below.
(1) a kind of with blended methods such as The compounds of this invention and solid carrier, liquid vehicle, gas phase carrier, poison baits, add as show the preparation assistant agent of promoting agent etc. and the method for preparating mixture alternatively.
(2) a kind of with a kind of method that does not comprise the base material of activeconstituents of The compounds of this invention dipping.
(3) a kind of method of The compounds of this invention and a kind of base material being mixed and form described mixture.
The content of The compounds of this invention in insecticide mixtures of the present invention depends on the type of preparation, yet these preparations comprise of the present inventionization and the thing of 0.001～99.9w/w% usually.
Example as preparations carrier comprises: solid carrier such as clay, diatomite, hydrated silica, talcum and its analogue, pottery, other inorganic ores (quartz, mica, gac, lime carbonate, montmorillonite) and chemical fertilizer are (such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, ammonium chloride); Liquid vehicle such as water, alcohol (as methyl alcohol, ethanol), ketone (as acetone, methyl ethyl ketone), aromatic hydrocarbon (as benzene, toluene, dimethylbenzene, ethylbenzene, methylnaphthalene), aliphatic hydrocarbon (as hexane, hexanaphthene, kerosene, gasoline), ester (ethyl acetate, butylacetate), nitrile (as acetonitrile, isopropyl cyanide), ether (as diisopropyl ether), acid amides is (as N, dinethylformamide, N,N-dimethylacetamide), halon (methylene dichloride, trichloroethane, tetracol phenixin), methyl-sulphoxide, vegetables oil (as soybean oil, rapeseed oil); Go into flon gas with the gas phase carrier, butagas, liquefied petroleum gas (LPG) (LPG), dimethylether and carbonic acid gas.
Show that the promoting agent example comprises alkyl-sulphate, alkylsulfonate, alkylaryl sulfonate, alkane aryl oxide, polyol ethers and sugar alcohol derivant.
Other assistant agent examples of preparation comprise sticking agent, dispersion agent and stablizer, typically: casein, gelatin, polysaccharide are (as starch, Sudan Gum-arabic, derivatived cellulose), lignin derivative, bentonite and water-soluble poly zoarium (as polyvinyl alcohol), polyacrylic acid, BHT (2,6-di-t-butyl-4-cresylol) and BHA (mixture of the 2-tertiary butyl-4-mequinol and the 3-tertiary butyl-4-mequinol).
The base material of mosquito-repellent incense circle for example, is the mixture of thick plant powder (as wood powder and pyrethrum marc) and tackiness agent (as Tabu powder (red nanmu powder), starch or gluten).
The base material of electric mosquito repellent tablet for example, is a kind of fiberboard of compacting velveteen, or the fiberboard of compacting paper pulp and velveteen mixture.
The base material of inflammable fumigant comprises that for example, exothermic agent is (as nitrate, nitrite, Potcrate, nitrocotton, ethyl cellulose, wood powder), the pyrolysis exciting agent is (as an alkali metal salt, alkaline earth salt, dichromate and chromic salt), oxygen source (as saltpetre), ignition dope is (as melanocyte, wheat starch), loose filler (as diatomite) and tackiness agent (synthetical glue).
The base material of chemical fumigant comprises, for example, exothermic agent (as alkali metalsulphide, hydrogen sulfide, calcium oxide), catalyzer (as carbonaceous material, carbonization can activated clay), organic foam agent (as azodicarbonamide, benzol sulfohydrazide, polystyrene) and filler (as natural or synthon).
The base material of non-heating volatile preparation comprises, for example, and THERMOPLASTIC RESINS and paper (as filter paper).
The base material of poison bait comprises that the bait composition is (as grain flour, vegetables oil, sugar, the crystal fibre element), antioxidant (as dibutyl paracresol), sanitas (as dehydroacetic acid (DHA)), be used to prevent children and the edible material (as red pepper powder) of pet mistake, insect attractive substance spices (as cheese spices, onion spice, peanut oil).
The method of Pest Control of the present invention is by insecticide mixtures of the present invention being applied to insect or the insect habitat is realized.
The application method of insecticide mixtures of the present invention is enumerated explanation hereinafter, and described method is suitably selected according to the type of insecticide mixtures or application site.
(1) a kind of method of using insecticide mixtures of the present invention, it is applied to insect or insect habitat.
(2) a kind ofly dilute the method that insecticidal compositions of the present invention is applied to insect or insect habitat then with solvent such as water.
In this case, with being configured to emulsus enriched material, wettable powder, easily the flow insecticidal compositions dilution of the present invention of preparation etc., so that the concentration of The compounds of this invention reaches 0.1～10000ppm.
(3) a kind of by method at a kind of activeconstituents of the insect habitat heating or the insecticide mixtures of the present invention that volatilizees at normal temperatures.
In these cases, the dosage of The compounds of this invention waits to determine according to type, time, place and using method, insect type, the infringement of sterilant of the present invention.But the dosage of The compounds of this invention is generally for planar applications 1～1000mg/m
2Or for space application 0.1～500mg/m
2
Insecticide mixtures of the present invention can with other sterilant, nematocides, soil pests control agent, mycocide, weedicide, plant-growth regulator, expellent, synergistic agent, fertilizer or soil redeposition be pre-mixed or non-blended situation under use simultaneously.
For the ease of using, carry and store, insecticide mixtures 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 mixture according to ordinary method as active insecticidal components, and promptly sterilant is used for removing mosquito, fly or cockroach class pest extremely.
Described mixture can be various forms of sterilants, comprises form domestic hygiene sterilants such as disc type insecticidal incense, electric mosquito repellent tablet, vaporizer mosquito liquid or aerosol.
Discharge fully and better reduce amount of application under the prerequisite of insecticidal effect in order to ensure effective constituent, improve its stability, make and use safety and environmental protection more, through discovering, can make insecticide mixtures of the present invention by aforesaid method, sterilant promptly of the present invention can guarantee the quality and technical index of product high-efficiency low-toxicity low residue, the sterilant that is made into simultaneously reduces the consumption of pesticide active ingredient greatly, improves the insecticidal effect of unit mixture.
The present invention also provides the above-mentioned application of mixture in desinsection, expelling parasite, " worm " of the present invention comprises harm people and animals and plants insects such as mosquito, fly, cockroach, agricultural pests bollworm, prodenia litura, cabbage caterpillar, aphid, comprises use agent such as fruit tree, vegetables, vegetation.
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 the specification of quality technical scope.
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 present invention researchs and develops a kind of new efficient fluorine-containing pyrethroid compound with independent intellectual property right, 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, agricultural pests, and require the synthesis technique of 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 quality degree of product.The following The compounds of this invention (I) that experiment showed, can reach the deinsectization effect of expection, and efficient, hypotoxicity, security are good.
Specific embodiments
Below in conjunction with embodiment the present invention is described, but the present invention not only is confined to following practical range.
Embodiment 1.1R-cis (Z)-2,2-dimethyl-3-(2-fluoro-1-propenyl)-cyclopropane-carboxylic acid or 1R-cis (Z)-2,2-dimethyl-3-(2-fluoro-1-propenyl)-cyclopropane acyl chlorides
(1) 1R-cis (Z)-2, the preparation of 2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane-carboxylic acid
0.5g tosic acid (PTSA) join and dissolved 5.78g 1R-cis (Z)-2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylic acid-1, the toluene of 1-dimethyl ethyl ester and 50ml.Reaction is till being heated to 120 ℃ of backflows.And then cool to 20 degree, and adopt the isopropyl ether dilution, washing, drying is filtered and is concentrated and obtains 4.40g 1R-cis (Z)-2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane-carboxylic acid.
(2) 1L-cis (Z)-2, the preparation of 2-dimethyl-3-(2-fluoro-1-propenyl)-cyclopropane acyl chlorides
1ml N, dinethylformamide (DMF) and 4.5ml carbonyl chloride (COCl)
2Be added into and be dissolved into 4.40g 1R-cis (Z)-2 in 0 ℃, 2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane-carboxylic acid and 50ml methylene dichloride, react 135min down at 20 ℃ again behind the stirring 45min down at 0 ℃, concentrate and reclaim methylene chloride, again distillment is dissolved into concentrate drying in the toluene, then adds 35ml formation acyl chlorides toluene liquid and be used for the back preparation.
Embodiment 2.1S-trans (E)-2,2-dimethyl-3-(2-fluoro-1-propenyl)-cyclopropane-carboxylic acid or 1S-trans
(E)-2,2-dimethyl-3-(2-fluoro-1-propenyl)-cyclopropane acyl chlorides:
(1) 1S-trans (E)-2,2-dimethyl-3-(2-fluoro-1-propenyl)-cyclopropane-carboxylic acid preparation:
1.2g tosic acid (PTSA) add the 1S-trans (E)-2 be dissolved in 13.86g, 2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane carboxylic acid-1, the toluene of 1-dimethyl ethyl ester and 140ml.Reaction is till being heated to 120 ℃ of backflows.And then cool to 20 ℃, and adopt the dilution of 250ml isopropyl ether, washing, drying is filtered and the concentrated 11g 1S-trans (E)-2,2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane-carboxylic acid of obtaining.
(2) 1S-trans (E)-2, the preparation of 2-dimethyl-3-(2-fluoro-1-propenyl)-cyclopropane acyl chlorides:
(COCl) of 3ml DMF and 10ml
2Be added into and be dissolved into 10g 1S-trans (E) 2 in 0 ℃, 2-dimethyl-3-(2-fluoro-1-propenyl) cyclopropane-carboxylic acid and 100ml methylene dichloride.React 135min down at 20 ℃ again behind the stirring 45min down at 0 ℃, 40 ℃ concentrate the recovery methylene chloride down, distillment are dissolved into concentrate drying in the toluene again, then add 55ml and form acyl chlorides toluene liquid, and the acyl chlorides toluene liquid of 1M/L prepares like this.
(preparation method of other carboxylic acids or acyl chlorides isomer is identical)
Synthesizing of embodiment 3 compounds (X1)
In the four-hole reaction flask of a 500ml, drop into 1-ethynyl-2-methylpent-2-enol 31.0g, pyridine 25.0g, be dissolved in 200ml toluene, stir, 5～10 ℃ drip 3-(2-fluoro-1-propenyl)-2 down, and 2-dimethyl cyclopropane carboxylic acid acyl chlorides 56.0g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 150ml 10% hydrochloric acid, use 150ml10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains-the 1-ethynyl-the 2-methylpent-2-thiazolinyl-3-(2-chloro-3,3,3-trifluoro allyl group)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 65.2g, and content is 91.2%, and yield is 85.6%.
The IR spectrogram shows υ-c=o 1750cm
-1The strong absorption peak and the υ-c-o-c-1180cm at place
-1And 1160cm
-1Two strong spikes explanation products in have the existence of ester group; υ-c=o is at 1720cm
-1About the explanation of strong broad peak the existence of carbonyl is arranged; At 2900cm
-1About with 1400cm
-1About characteristic peak explanation υ-
CH3, υ-
CH2-existence; 3080cm-1 and 3030cm
-1It is that the stretching vibration of υ-c=c-causes that two strong and spikes are arranged, at 1650cm
-1Intensity spikes υ-c=c-characteristic absorbance; The GC/MS spectrogram shows that this compound molecular weight is 278.3; The NMR spectrogram prove in this compound H in the position in the structure shown in above-mentioned structural formula.NMR (
1H, CDCl
3) δ: 5.72 (s, 1H); 5.44 (m, 1H); 4.60 (d, 1H); 3.55 (s, 1H); 1.95～2.05 (m, 2H); 1.80 (s, 3H); 1.71 (s, 3H); 1.65 (d, 1H); 1.22 (d, 1H); 1.06 (t, 3H); 1.01 (s, 6H); More than three kinds of spectrograms prove that jointly this compound is: 1-ethynyl-2-methylpent-2-thiazolinyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
17H
23O
2F, product are weak yellow liquid.
Synthesizing of embodiment 4 compounds (X2)
In the four-hole reaction flask of a 500ml, drop into [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methylol 42.0g, pyridine 25.0g, be dissolved in 200ml toluene, stir, 5～10 ℃ drip 1L-3-(2-fluoro-1-propenyl)-2 down, 2-dimethyl cyclopropane carboxylic acid 45g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 150ml 10% hydrochloric acid, use 150ml 10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains 1L-[2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 74.8g, content is 92.3%, and yield is 85.8%.
The IR spectrogram shows υ-c=o 1750cm
-1The strong absorption peak and the υ-c-o-c-1180cm at place
-1And 1160cm
-1Two strong spikes explanation products in have the existence of ester group; υ-c=o is at 1700～1730cm
-1About the explanation of strong broad peak the existence of carbonyl is arranged; υ-CN is at 2100cm
-1About in strong absorption peak exist; At 2900cm
-1About with 1400cm
-1About characteristic peak explanation υ-
CH3, υ-
CH2-existence; The GC/MS spectrogram shows that this compound molecular weight is 322.3; The NMR spectrogram prove in this compound H in the position in the structure shown in above-mentioned structural formula.NMR (
1H, CDCl
3) δ: 5.96 (s, 2H); 4.60 (d, 1H); 4.05 (s, 2H); 3.92 (s, 2H); 3.08 (s, 1H); 1.75 (s, 3H); 1.54 (d, 1H); 1.10 (d, 1H); 1.01 (s, 6H); More than three kinds of spectrograms prove that jointly this compound is: [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
16H
19FN
2O
4, product is a weak yellow liquid.
Synthesizing of embodiment 5 compounds (X3)
In the four-hole reaction flask of a 500ml, drop into 2,3,5,6-tetrafluoro-4-xylyl alcohol 48.5g, pyridine 25.0g is dissolved in 200ml toluene, stirs, 5～10 ℃ drip 1R down, 3S-3-(2-fluoro-1-propenyl)-2,2-dimethylcyclopropane acyl chlorides 49g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 150ml 10% hydrochloric acid, use 150ml 10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains 1R, 3S-2,3,5,6-tetrafluoro-4-methyl-benzyl-trans-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 84.6g, and content is 92.1%, and yield is 89.5%.
The IR spectrogram shows υ-c=o 1750cm
-1The strong absorption peak and the υ-c-o-c-1180cm at place
-1And 1160cm
-1Two strong spikes explanation products in have the existence of ester group; υ-c=o is at 1720cm
-1About the explanation of strong broad peak the existence of carbonyl is arranged; At 2900cm
-1About with 1400cm
-1About characteristic peak explanation υ-
CH3, υ-
CH2-existence; 1600cm
-1With 1500cm
-1There is υ-Ar-phenyl ring charateristic avsorption band at the place; The GC/MS spectrogram shows that this compound molecular weight is 348.1; The NMR spectrogram prove in this compound H in the position in the structure shown in above-mentioned structural formula.NMR (
1H, CDCl
3) δ: 5.35 (s, 2H); 4.60 (d, 1H); 2.38 (s, 3H); 1.75 (s, 3H); 1.54 (d, 1H); 1.10 (d, 1H); 1.01 (s, 6H); More than three kinds of spectrograms prove that jointly this compound is: 2,3,5,6-tetrafluoro-4-methyl-benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
17H
17F
5O
2, product is a weak yellow liquid.
Synthesizing of embodiment 6 compounds (X4)
In the four-hole reaction flask of a 500ml, drop into 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol 52.5g, pyridine 25.0g, be dissolved in 200ml toluene, stir, 5～10 ℃ drip 1S-trans (Z)-3-(2-fluoro-1-propenyl)-2 down, 2-dimethylcyclopropane acyl chlorides 48g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 150ml 10% hydrochloric acid, use 150ml 10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains 1S-2,3,5,6-tetrafluoro-4-methoxy-benzyl-trans (Z)-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 85.7g, and content is 91.5%, and yield is 86.2%.
The IR spectrogram shows υ-c=o 1750cm
-1The strong absorption peak and the υ-c-o-c-1180cm at place
-1And 1160cm
-1Two strong spikes explanation products in have the existence of ester group; υ-c=o is at 1720cm
-1About the explanation of strong broad peak the existence of carbonyl is arranged; At 2900cm
-1About with 1400cm
-1About characteristic peak explanation υ-
CH3, υ-
CH2-existence; 1600cm
-1With 1500cm
-1There is υ-Ar-phenyl ring charateristic avsorption band at the place; The GC/MS spectrogram shows that this compound molecular weight is 364.1; The NMR spectrogram prove in this compound H in the position in the structure shown in above-mentioned structural formula.NMR (
1H, CDCl
3) δ: 5.35 (s, 2H); 4.60 (d, 1H); 3.80 (s, 3H); 1.71 (s, 3H); 1.54 (d, 1H); 1.10 (d, 1H); 1.01 (s, 6H); More than three kinds of spectrograms prove that jointly this compound is: 2,3,5,6-tetrafluoro-4-methoxy-benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
17H
17F
5O
3, product is a deep yellow liquid.
Synthesizing of embodiment 7 compounds (X5)
In the four-hole reaction flask of a 500ml, drop into 2,3,5,6-tetrafluorobenzyl alcohol 45.0g, pyridine 25.0g is dissolved in 200ml toluene, stirs, 5～10 ℃ drip 1S-cis-3-(2-fluoro-1-propenyl)-2 down, and 2-dimethylcyclopropane acyl chlorides 48g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 150ml 10% hydrochloric acid, use 150ml 10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains 1S-2, and 3,5,6-ptfe benzyl-cis-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 77.3g, and content is 91.2%, and yield is 84.4%.
The IR spectrogram shows υ-c=o 1750cm
-1The strong absorption peak and the υ-c-o-c-1180cm at place
-1And 1160cm
-1Two strong spikes explanation products in have the existence of ester group; υ-c=o is at 1720cm
-1About the explanation of strong broad peak the existence of carbonyl is arranged; At 2900cm
-1About with 1400cm
-1About characteristic peak explanation υ-
CH3, υ-
CH2-existence; 1600cm
-1With 1500cm
-1There is υ-Ar-phenyl ring charateristic avsorption band at the place; The GC/MS spectrogram shows that this compound molecular weight is 334.2; The NMR spectrogram prove in this compound H in the position in the structure shown in above-mentioned structural formula.NMR (
1H, CDCl
3) δ: 6.60 (m, 1H); 5.35 (s, 2H); 4.60 (d, 1H); 1.70 (s, 3H); 1.54 (d, 1H); 1.10 (d, 1H); 1.01 (s, 6H); More than three kinds of spectrograms prove that jointly this compound is: 2,3,5,6-ptfe benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
16H
15F
5O
2, product is a weak yellow liquid.
Synthesizing of embodiment 8 compounds (X6)
In the four-hole reaction flask of a 500ml, drop into 2,3,5,6-tetrafluoro-4-methoxymethyl benzylalcohol 50.0g, pyridine 25.0g, be dissolved in 200ml toluene, stir, 5～10 ℃ drip 3-(2-fluoro-1-propenyl)-2 down, 2-dimethylcyclopropane acyl chlorides 44.5g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 150ml 10% hydrochloric acid, use 150ml 10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, weight is 81.1g, and content is 91.7%, and yield is 87.9%.
The IR spectrogram shows υ-c=o 1750cm
-1The strong absorption peak and the υ-c-o-c-1180cm at place
-1And 1160cm
-1Two strong spikes explanation products in have the existence of ester group; At 2900cm
-1About with 1400cm
-1About characteristic peak explanation υ-
CH3, υ-
CH2-existence; 3080cm-1 and 3030cm
-1It is that the stretching vibration of υ-c=c-causes that two strong and spikes are arranged, at 1650cm
-1Intensity spikes υ-c=c-characteristic absorbance; The GC/MS spectrogram shows that this compound molecular weight is 378.1; The NMR spectrogram prove in this compound H in the position in the structure shown in above-mentioned structural formula.NMR (
1H, CDCl
3) δ: 5.35 (s, 2H); 4.80 (s, 2H); 4.60 (d, 1H); 3.35 (s, 3H); 1.70 (s, 3H); 1.54 (d, 1H); 1.10 (d, 1H); 1.01 (s, 6H); More than three kinds of spectrograms prove that jointly this compound is: 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, molecular formula C
18H
19F
5O
3, product is pale brown look liquid.
Synthesizing of embodiment 9 compounds (X7)
In the four-hole reaction flask of a 500ml, drop into 2-methyl-3-phenyl benzylalcohol 49.5g, pyridine 25.0g, be dissolved in 200ml toluene, stir, 5～10 ℃ drip E-3-(2-fluoro-1-propenyl)-2 down, 2-dimethyl cyclopropane carboxylic acid 45g is warming up to 25 ℃ of reactions 2 hours after dropwising.Wash at twice with 150ml 10% hydrochloric acid, use 150ml 10%NaHCO again
3Washing is at twice told toluene layer and is purified solvent toluene in the 0.08Mpa heating, obtains 2-methyl-3-phenylbenzyl-E-3-(2-fluoro-1-propenyl)-2,2 dimethyl cyclopropane carboxylic acid's esters, and weight is 82.6g, and content is 91.2%, and yield is 85.6%.
The IR spectrogram shows that the strong absorption peak at υ-c=o 1750cm-1 place and two strong spikes of υ-c-o-c-1180cm-1 and 1160cm-1 illustrate the existence that has ester group in the products; The strong broad peak explanation of υ-c=o about 1720cm-1 has the existence of carbonyl; About 2900cm-1 with 1400cm-1 about characteristic peak explanation υ-CH
3, υ-CH
2-existence; There is υ-Ar-phenyl ring charateristic avsorption band at 1600cm-1 and 1500cm-1 place; The GC/MS spectrogram shows that this compound molecular weight is 352.2; The NMR spectrogram prove in this compound H in the position in the structure shown in above-mentioned structural formula.NMR (1H, CDCl3) δ: 7.20～7.60 (m, 7H); 5.35 (s, 2H); 4.60 (d, 1H); 2.70 (s, 3H); 1.70 (s, 3H); 1.54 (d, 1H); 1.10 (d, 1H); 1.01 (s, 6H); More than three kinds of spectrograms prove that jointly this compound is: 2-methyl-3-phenylbenzyl-3-(2-fluoro-1-propenyl)-2,2 dimethyl cyclopropane carboxylic acid's esters, molecular formula C
23H
25FO
2, product is pale brown look liquid.
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 line spices shape line spices base material then.
The compound of the method preparation of embodiment 1 is dissolved into concentration in kerosene be 0.04-0.6w/v% solution.
Evenly drip the above-mentioned solution of 4ml on above-mentioned line spices base material, placement got final product in about 2～5 hours under the room temperature.
The product diameter 12.0cm that obtains, thick 3.5-5mm, two in a cover, the heavily about 40g of a cover.
The inventor is a drum method well known in the art with experimental technique, and coiled mosquito-repellent incense carries 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.
Table a. drum method effect experiment result (culex) (formulation: mosquito-repellent incense)
| Sequence number | The sample title | Content (%) wt | ??KT 50(min) | 24h mortality ratio (%) |
| ??1 | Compound (X1) | ??0.04 | ??2′21″ | ??100 |
| ??2 | Compound (X2) | ??0.04 | ??4′54″ | ??100 |
| ??3 | Compound (X3) | ??0.04 | ??4′04″ | ??98 |
| ??4 | Compound (X4) | ??0.05 | ??3′33″ | ??100 |
| ??5 | Compound (X5) | ??0.05 | ??3′05″ | ??95 |
| ??6 | Compound (X6) | ??0.04 | ??3′13″ | ??100 |
| ??7 | Compound (X7) | ??0.04 | ??4′55″ | ??100 |
| ??8 | Transfluthrin | ??0.04 | ??7′45″ | ??90 |
Compound of the present invention is at same KT
50Under the index prerequisite of 24 hours lethality rates, by a large amount of experiments, the usage quantity general formula is that the relative effectivenes of compound of (I) is at more than 1～2 times of transfluthrin.The content that experiment showed, The compounds of this invention when 0.01～0.5% concentration more, and the sterilant effect that is applied to different dosage form is all very outstanding.Above medicine is the biological effect experiment to mosquito, near or reach existing market medication effect, be the kind that is worthy of popularization.They can replace the product application of allethrin series chrysanthemum ester in formulation sterilants such as mosquito-repellent incenses.
Application Example 2
With the solution impregnating carrier porous pad that contains arbitrary compound of 4mg compound (X1) 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 3
With the solution impregnating carrier porous pad that contains arbitrary compound of 4mg compound (X2) 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 4
With the solution impregnating carrier porous pad that contains arbitrary compound of 4mg compound (X3) 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 arbitrary compound of 4mg compound (X4) 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 chlorempenthrin electric mosquito repellent tablet of application example 2-5 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 GB 13917.5-92, 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 b:
The electric mat of table b. The compounds of this invention preparation and the effect of the alkynes third chrysanthemum ester electric mat are relatively
| The compound composition | Effective content (mg/ sheet) | ??KT 50(min) |
| ??1h | ?2h | ?4h | ??6h | ?8h | ||
| ??X1 | ??4 | ??3′21″ | ?3′45″ | ?4′56″ | ??4′21″ | ?5′43″ |
| ??X2 | ??4 | ??3′32″ | ?4′25″ | ?4′78″ | ??4′55″ | ?5′47″ |
| ??X3 | ??4 | ??4′34″ | ?5′20″ | ?5′34″ | ??4′67″ | ?5′67″ |
| ??X4 | ??4 | ??3′53″ | ?4′23″ | ?4′34 | ??4′23″ | ?4′43″ |
| The alkynes third chrysanthemum ester | ??10 | ??6′83″ | ?7′32″ | ?8′69″ | ??8′90″ | ?8′34″ |
The result shows: with The compounds of this invention (I) be the electric mat relative effectivenes for preparing of former medicine 5～10 times at the alkynes third chrysanthemum ester anti-mosquito incense sheet.
Application Example 6
With 0.4 part of compounds X 5 (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%.
Application Example 7
With 0.4 part of compounds X 6 (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 GB13917.6-2009, 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 c:
The vaporizer mosquito liquid of table c. 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 (X5), (X6) be that the relative effectivenes of the vaporizer mosquito liquid for preparing of former medicine is about 5 times of the alkynes third chrysanthemum ester vaporizer mosquito liquid.
Application Example 8
Kerosene, propellent, casting resin with 0.15 weight part compounds X 6 (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 0.02w/w%.
Application Example 9
Kerosene, propellent, filling with 0.15 weight part compounds X 6 (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 and 9 is carried out efficacy testing to insect according to GB13917.2-2009, 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 d as a result.
The insect aerosol of table d The compounds of this invention preparation is to the insect killing effect of fly, cockroach
| Numbering | Insect | ??KT 50(fly/cockroach) |
| Compounds X 6 | Fly | ??3′42″ |
| Compounds X 6 | Cockroach | ??3′42″ |
The result shows: the aerosol of The compounds of this invention X6 preparation has good insect killing effect to fly, cockroach.
The above results shows, herein Fa Ming chemicals (I) 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 3～5 times with respect to the cis product simultaneously, helps being used in enormous quantities the application of domestic hygiene preparation.
Application Example 10
This product is stable to light, has and tags more by force and stomach poison function.Insects such as multiple larva of lepidopteran and aphid are had good result, and drug effect is rapid, and the longevity of residure is long, is applicable to cotton, tobacco, vegetables, soybean, peanut, seeding corn and other crops.With chemicals 5g of the present invention and 85g solvent (comprising dimethylbenzene, toluene etc.), the 10g emulsifying agent is formulated as 5% missible oil.To 500～1000 times of sprayings of water dilution, promptly can be used for preventing and treating the farmland agricultural chemicals.
Claims (8)
1. fluorine-containing pyrethroid compound has following general structural formula (I):
Wherein R is (a) 1-ethynyl-2-methylpent-2-thiazolinyl or (b) 2,5-dioxy-3-(2-propynyl)-1-imidazolidyl methyl or (c) 2,3,5,6-tetrafluoro-4-methyl-benzyl or (d) 2,3,5,6-tetrafluoro-4-methoxy-benzyl or (e) 2,3,5,6-ptfe benzyl or (f) 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl or (g) 2-methyl-3 phenylbenzyl, its structural formula is respectively:
When R is (a) 1-ethynyl-2-methylpent-2-thiazolinyl, compound (X1) is 1-ethynyl-2-methylpent-2-thiazolinyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (b) 2,5-dioxy-3-(2-propynyl)-1-imidazolidyl methyl, compound (X2) are [2,5-dioxy-3-(2-propynyl)]-1-imidazolidyl methyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (c) 2,3,5,6-tetrafluoro-4-methyl-benzyl, compound (X3) is 2,3,5,6-tetrafluoro-4-methyl-benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (d) 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl, compound (X4) is 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester; .
When R is (e) 2,3,5, the 6-ptfe benzyl, compound (X5) is 2,3,5,6-ptfe benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
When R is (f) 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl, compound (X6) is 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl-3-(2-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester
When R is (g) 2-methyl-3-phenylbenzyl, compound (X7) is 2-methyl-3-phenylbenzyl-3-(2-fluoro-1-propenyl)-2,2 methyl cyclopropane carboxylicesterss.
2. according to the described a kind of fluorine-containing pyrethroid compound of claim 1, it is characterized in that cyclopropane 1 in the The compounds of this invention general formula (I), 3 chiral carbon atoms have the left and right sides optically-active isomer of optical isomer levo form S body and dextrorotatory form R body, also have geometrical isomer Trans, Cis, Z and E on the cyclopropane ring and on the carbon-carbon double bond; Each compound comprises all and has the active optical isomer of pest control, geometrical isomer and composition thereof.
3. synthetic method according to a kind of fluorine-containing pyrethroid compound described in claim 1 or 2 is characterized in that:
With general formula (A) expression acyl chlorides
With general formula (B) expression carboxylic acid
With general formula (C) expression alcohol
HO-R(C)
Wherein R is by the group of formula (a) and (b), (c), (d), (e), (f), (g) expression.
General formula (A) or general formula (B) just can obtain formula (I) series compound with the alcohol of general formula (C) expression by esterification.
4. according to the purposes of claim 1 or 2 described a kind of fluorine-containing pyrethroid compounds, it is characterized in that monomer, the mixture that will have active each compound are mixed with various formulation sterilants and are applied to domestic hygiene medication and agriculture medication aspect.
5. according to the purposes of the described a kind of fluorine-containing pyrethroid compound of claim 4, the formulation that it is characterized in that indication is that to contain the monomer of each compound or mixture be active ingredient
Missible oil, emulsifiable concentrate, wettable powder, mobile preparation (as
Water emulsion), pulvis, granule, aerosol, heating volatile preparation, heating fumigating agent, smoke-like preparation, ultra-low volume (ULV) preparation and poison bait.
6. the purposes of a kind of fluorine-containing pyrethroid compound according to claim 4, it is characterized in that medication that above-mentioned various formulation is applied to domestic hygiene is meant the preparation of the household insect that is used to prevent and treat mosquito, fly, Groton bug, ant or louse aspect, as the disc type insecticidal incense, electric mosquito repellent tablet, vaporizer mosquito liquid or the agent of desinsection gas evil.
7. according to the purposes of the described a kind of fluorine-containing pyrethroid compound of claim 4, it is characterized in that above-mentioned various formulation is applied in the pharmaceutical preparation that agriculture medicament is meant multidisciplinary insects such as bollworm twill in control fruit tree, the vegetables cash crop vegetation, noctuid, cabbage caterpillar, aphid.
8. according to the purposes of the described a kind of fluorine-containing pyrethroid compound of claim 5, the composition of its feature aspect desinsection, acaricidal activity constitutes, comprise that the weight ratio of compound effective constituent from 0.001% to 99.9% of general formula (I) and other subsidiary material are prepared from formulation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673961A (en) * | 2016-08-01 | 2018-02-09 | 江苏优士化学有限公司 | A kind of clean preparation method of pyrethroid intermediate chrysanthemumic acid |
| CN109776327A (en) * | 2019-02-27 | 2019-05-21 | 黄山学院 | First chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound, preparation method and application |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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
- 2010-05-14 CN CN 201010172052 patent/CN101830805A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107673961A (en) * | 2016-08-01 | 2018-02-09 | 江苏优士化学有限公司 | A kind of clean preparation method of pyrethroid intermediate chrysanthemumic acid |
| 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 |
| CN109776327A (en) * | 2019-02-27 | 2019-05-21 | 黄山学院 | First chlorine chrysanthemumic acid polyfluoro benzylalcohol chrysanthemum ester type compound, preparation method and application |
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