CN101665433B - New pyrethroid compound and preparation method and application - Google Patents
New pyrethroid compound and preparation method and application Download PDFInfo
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- CN101665433B CN101665433B CN 200910142186 CN200910142186A CN101665433B CN 101665433 B CN101665433 B CN 101665433B CN 200910142186 CN200910142186 CN 200910142186 CN 200910142186 A CN200910142186 A CN 200910142186A CN 101665433 B CN101665433 B CN 101665433B
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Abstract
The invention provides a pyrethroid compound which is a stereoisomer of 2,3,5,6-tetrafluoro-4-methoxybenzyl-3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropane carboxylate. The compound is characterized in that the structure of the compound is shown in formula (A), wherein the carbon-carbon double bond in the carboxylic acid part of the formula (A) is Z configuration, the absolute configuration of the 1-site of cyclopropane is R configuration; the compound is 2,3,5,6-tetrafluoro-4-methoxybenzyl-1R-(Z)-3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropane carboxylate. The pyrethroid compound has high activity and significant effect for controlling the pestiferous pests. The invention also provides a preparation method and an application of the pyrethroid compound.
Description
Technical field
The present invention relates to a kind of pyrethroid compound, and preparation method thereof with the control sanitary insect pest application.
Background technology
Pyrethroid coumpound can be used for mosquito control, and has higher insecticidal activity, and this is widely known by the people.Because it has efficiently, low toxicity, low residue, environment compatibility are good, be widely used in the prevention and control field of sanitary insect pest.We by the structure of modification to traditional pyrethroid acid, alcohol moiety, have formed the fluorine-containing pyrethroid compound of series of novel in CN101381306A.The preliminary test of pesticide effectiveness of these compounds shows to have good insecticidal activity, knocks down soon, and lethality rate is high.But these new pyrethroid compounds more or less some defectives of existence also on basic insecticidal activity or vapour pressure, we continue further investigation on the basis of working before, find 2,3,5,6-tetrafluoro-4-methoxy-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester had both had good basic insecticidal activity, and its vapour pressure also is higher than most pyrethroids of present use, the compounds of this invention vapour pressure 2176.6Pa＞chlorempenthrin 1931.0Pa＞transfluthrin 1978.6Pa＞methoxy benzyl Flumethrin 1323.8Pa＞dimefluthrin 1163.3Pa＞Prallethrin 940.9Pa, the vapour pressure here be with Donovan method (being published in Journal of Chromatography A by Stephen F.Donovan, the method for reporting in " New method for estinating vapor pressure by the use of gas chromatography (estimating the novel method of vapour pressure with gas-chromatography) " literary composition of 749 (1996) 123-129) obtain 25 ℃ vapour pressure.The above advantage of the compounds of this invention has overcome the defective of original compound, has well satisfied the needs of the mosquito repellent product of our development of new normal temperature volatilizations.
On the other hand; along with people are more and more higher to the requirement of environmental protection, the high biological activity body of agricultural chemicals more and more causes people's attention, and pyrethroid has a plurality of optical isomers usually; biological activity is widely different between each isomer, therefore needs the highly active isomer of research preparation.From the angle of environmental protection, use highly active isomer can under the prerequisite that does not reduce drug effect, reduce the dose of using, thereby reduce the toxicity to non-target organism, improve security, reduce the left drug environmental pollution.Based on such thinking, we further study each stereomeric biological activity of this compound, and 2 unsymmetrical carbons are arranged on this compound cyclopropane, have isomer, and there is carbon-carbon double bond in carboxylic moiety, also have Z, E configuration isomery.We found through experiments, and the compound the when absolute steric configuration that cyclopropane is 1 is the configuration of R has the drug effect higher than S configuration of compound; Further experiment shows, compound drug effect when the carbon-carbon double bond that carboxylic moiety exists is the Z configuration is better than the compound of E configuration, that is to say such as 2 of (A) formula, 3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester is a highly active isomer.
Summary of the invention
Primary and foremost purpose of the present invention just provides a kind of highly active pyrethroid compound that has, and the control of sanitary insect pest is had better effect.
The present invention also provides the preparation method of described pyrethroid compound and in the application in control sanitary insect pest field.
The objective of the invention is to be achieved through the following technical solutions:
A kind of pyrethroid compound is provided, 2,3,5,6-tetrafluoro-4-methoxy-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2, the steric isomer of 2-dimethyl cyclopropane carboxylic acid ester, described compound structure is shown in (A) formula, the carbon-carbon double bond of carboxylic moiety is the Z configuration in its Chinese style (A), and the absolute steric configuration of 1 of cyclopropane is the R configuration; Be that described compound is 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
Pyrethroid compound shown in the above-mentioned formula (A) exists because the cyclopropane planar unsymmetrical has cis-trans-isomer.Therefore, described pyrethroid compound can be that one of described cis-trans-isomer (both can be 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, trans-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester also can be 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, cis-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester), or these two kinds of mixtures that isomer mixes mutually with arbitrary proportion.The caused drug effect difference of this isomery is not remarkable, and our research finds that wherein the trans-isomer(ide) drug effect slightly is better than cis-isomeride.
A kind of synthetic method of described pyrethroid compound is: use suc as formula the 1R-(Z) shown in (B)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid and 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol is according to 0.8～1.2: 1 mol ratio, in the organic solvents such as toluene or hexanaphthene, under 60-130 ℃, sulfuric acid or Catalyzed by p-Toluenesulfonic Acid, carry out esterification and obtain; Wherein, the mol ratio of catalyst sulfuric acid or tosic acid and 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol is 0.01～0.1: 1.
The another kind of synthetic method of described pyrethroid compound is: by the 1R-(Z) shown in the formula (B)-3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid obtains 1R-(Z)-3-(3,3 through the chloride reagent chloride, 3-three fluoro-1-propenyl)-2, behind the 2-dimethyl cyclopropane carboxylic acid acyl chlorides, again with 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol reaction makes; Wherein, described chloride reagent can be sulfur oxychloride.
The compound 1R-(Z) of described formula (B)-3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid can be synthetic by several different methods of the prior art, preferably by 1R-3-(3,3,3-, three fluoro-1-propenyl)-2, the separation of 2-dimethyl cyclopropane carboxylic acid recrystallization obtains.Wherein, the used solvent of recrystallization is methanol-water, methyl alcohol: the weight ratio of water is 0.1～10: 1; 1R-3-(3,3,3-, three fluoro-1-propenyl)-2, the weight ratio of 2-dimethyl cyclopropane carboxylic acid and used recrystallization solvent is 0.05～0.1: 1.
Described 1R-3-(3,3,3-, three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid can be synthetic by several different methods of the prior art, preferably by the aldehydo-ester shown in (C) formula and wittig reagent (C
6H
5)
3P
+-CH
2CF
3 -In the anhydrous organic solvents such as tetrahydrofuran (THF) with 0.8～1.2: 1 mol ratio was 0～40 ℃ of lower reaction 5～20 hours, and the compound that obtains formula (D) is hydrolyzed and obtains.
(C) R=CH wherein
3, CH
2CH
3(D) R=CH wherein
3, CH
2CH
3
The hydrolysis of the compound shown in the described formula (D) can be to be hydrolyzed in diluted acid or to be hydrolyzed in sig water, then with mineral acid acidifyings such as sulfuric acid, can obtain 1R-3-(3,3,3-, three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid.
The present invention also provides described pyrethroid compound except the application of killing aspect the sanitary insect pests such as mosquito, fly or Groton bug.
Described application be with the described pyrethroid compound of formula (A) as former medicine, be prepared into various forms of sterilants, be used for except killing mosquito, fly or Groton bug.
Because described pyrethroid compound has than the existing conventional higher vapour pressure of pyrethroid of using, therefore can be made into the various desinsection formulations under heated volatile, such as disc type insecticidal incense, electric mosquito repellent tablet or electric liquid device etc., or make the filter paper ribbon formulation that is fit at normal temperatures volatilization use.
Embodiment
The below explains technical scheme of the present invention and effect in detail with the form of embodiment, but the present invention is not limited to following examples.
Preparation Example 1:
Suitable inverse ratio is 1: 1 1R-3-(3,3,3-, three fluoro-1-propenyl)-2, and the 2-dimethyl cyclopropane carboxylic acid's is synthetic
In the four-hole bottle of a 250ml, input is 1: 1 1R-3-aldehyde radical-2 along inverse ratio, 2-dimethyl cyclopropane carboxylic acid methyl esters 15.6g (0.1mol), 50ml anhydrous tetrahydro furan, add again the 0.5g potassium tert.-butoxide, drip while stirring 34.5g (0.1mol) (C under 5 ℃
6H
5)
3P
+-CH
2CF
3 -Be dissolved in the suspension liquid of 80ml tetrahydrofuran (THF), drip in 2 hours and finish, then be warming up to 20 ℃ of reactions 8 hours.Slough tetrahydrofuran (THF) under the 50mmHg negative pressure, add 100ml toluene, respectively with 200ml washing twice, tell toluene layer and add the sodium hydroxide solution of 100g 10%, stir lower 80 ℃ of reactions 2 hours that are heated to, be cooled to room temperature, divide and remove toluene layer.Water layer is transferred in the 250ml there-necked flask, and lower 30% the sulphuric acid soln 100g that drips of ice-water bath insulation keeps temperature to be lower than 5 ℃, dripping to finish has a large amount of canescence flockss to separate out, filter, get 20ml clear water washing solid twice, obtain being heated to 100 ℃ under the negative pressure after air-dry to purify solvent toluene, obtaining compound is 1: 1 1R-3-(3 along inverse ratio, 3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 16.4g, content is 92.3%, yield 72.7%.
Preparation Example 2:
Preparation is 1: 1 1R-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2 along inverse ratio, the 2-dimethyl cyclopropane carboxylic acid
In the beaker of a 100ml, drop into the 1R-3-(3 of gained among the embodiment 1,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 16.4g (92.3%), the methanol-water solution 30g that adds again 1: 1 weight ratio 40 ℃ of lower stirrings 30 minutes, filters, the gained solid stirred 30 minutes under 30 ℃ in the methanol-water solution that drops into 1: 2 weight ratio of 15g, again filter, the gained solid again with the washing of 5ml clear water once namely gets compound after air-dry and along inverse ratio is 1: 1 1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 5.8g, content 98.7%.The mother liquor that merges 2 filtrations, being concentrated at thin-film evaporator under 40 ℃, 100mmHg negative pressure just has solid to separate out, fetch concentrated solution and be cooled to 5 ℃, have again some solids to separate out, filter, air-dry obtaining along inverse ratio is 1: 1 1R-(E)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 4.2g, content 95.1%.
Preparation Example 3:
Along inverse ratio be 1: 12,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 1)
In the flask of a 500ml, input is 1: 1 1R-(Z)-3-(3 according to the suitable inverse ratio of embodiment 2 methods preparations, 3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol), 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol 21.0g (0.1mol), 180ml toluene is loaded onto water trap, add again the 0.1g tosic acid, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, with the 100g washing once, dilute hydrochloric acid with 100g 5% washs once again, uses the sodium hydrogen carbonate solution washing of 100g 5% once, and last 100g water washs once again, collecting toluene layer is heated to 100 ℃ and purifies solvent toluene and obtain 2 under the 10mmHg negative pressure, 3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 1) 35.6g, content 98.3%, yield 90.7% is 1: 1 along inverse ratio.The molecular formula of this compound: C
17H
15F
7O
3Molecular weight 400, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); (1.69 d, 1H); (2.44 m, 1H); (3.82 s, 3H); (5.30 s, 2H); (5.60 m, 1H); (5.80 m, 1H), specific rotation α=+ 33.4 degree.
Preparation Example 4:
Control compounds along inverse ratio be 1: 12,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(E)-3-(3,3,3-, three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 2)
According to the method in the Preparation Example 3, with suitable 1: 1 1R-of inverse ratio (E)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol) is with 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol 21.0g (0.1mol) reaction obtains 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(E)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 2) 34.5g, content 97.9%.The molecular formula of this compound: C
17H
15F
7O
3Molecular weight 400, the nuclear magnetic resonance spectrum nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); (1.71 d, 1H); (2.12 m, 1H); (3.81 s, 3H); (5.27 m, 2H); (5.79 m, 1H); (6.03 m, 1H), specific rotation α=+ 33.4 degree.
Preparation Example 5:
Control compounds along inverse ratio be 1: 12,3,5,6-tetrafluoro-4-methoxy-benzyl-1S-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 3) and along inverse ratio be 1: 12,3,5,6-tetrafluoro-4-methoxy-benzyl-1S-(E)-3-(3,3,3-three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 4)
According to the method in the Preparation Example 1, starting raw material is changed work along 1: 1 1S-3-aldehyde radical-2 of inverse ratio, 2-dimethyl cyclopropane carboxylic acid methyl esters can make 1S-3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid, obtain respectively 1S-(Z)-3-(3 by embodiment 2 described method recrystallizations, 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid and 1S-(E)-3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid.
According to the method in the Preparation Example 3, with 1S-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid is with 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol reaction obtains 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1S-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 3).The molecular formula of this compound: C
17H
15F
7O
3Molecular weight 400, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); (1.69 d, 1H); (2.44 m, 1H); (3.82 s, 3H); (5.30 s, 2H); (5.60 m, 1H); (5.80 m, 1H), specific rotation α=-33.4 degree.
With suitable 1: 1 1S-of inverse ratio (E)-3-(3,3,3-, three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid is with 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol reaction obtains 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1S-(E)-3-(3,3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 4).The molecular formula of this compound: C
17H
15F
7O
3Molecular weight 400, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); (1.71 d, 1H); (2.12 m, 1H); (3.81 s, 3H); (5.27 m, 2H); (5.79 m, 1H); (6.03 m, 1H), specific rotation α=-33.4 degree.
Preparation Example 6:
2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, cis-(Z)-and 3-(3,3,3-, three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 5)
According to the method in the Preparation Example 3, use 1R, cis-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol), with 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol 21.0g (0.1mol) reaction obtains 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, cis-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 5) 33.9g, content 98.2%.The molecular formula of this compound: C
17H
15F
7O
3Molecular weight 400, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); (1.69 d, 1H); (2.44 m, 1H); (3.82 s, 3H); (5.30 s, 2H); (5.60 m, 1H); (5.80 m, 1H), the coupling constant 3J=8.9Hz of two H on the cyclopropane plane, specific rotation α=+ 33.4 degree.
Preparation Example 7:
2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, trans-(Z)-and 3-(3,3,3-, three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 6)
According to the method in the Preparation Example 3, use 1R, trans-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol), with 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol 21.0g (0.1mol) reaction obtains 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, cis-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 6) 34.2g, content 98.0%.The molecular formula of this compound: C
17H
15F
7O
3Molecular weight 400, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); (1.69 d, 1H); (2.44 m, 1H); (3.82 s, 3H); (5.30 s, 2H); (5.60 m, 1H); (5.80 m, 1H), the coupling constant 3J=5.4Hz of two H on the cyclopropane plane, specific rotation α=+ 33.4 degree.
Preparation Example 8:
Along inverse ratio be 1: 92,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 7)
According to the method in the Preparation Example 3, with the 1R-(Z)-3-(3 that along inverse ratio is 1: 9,3,3-three fluoro-1-propenyl)-2, (0.1mol is 1: 9 1R-3-aldehyde radical-2 by starting raw material along inverse ratio to 2-dimethyl cyclopropane carboxylic acid 20.8g, 2-dimethyl cyclopropane carboxylic acid methyl esters begins preparation), with 2,3,5, the reaction of 6-tetrafluoro-4-methoxyl group benzylalcohol 21.0g (0.1mol) obtain along inverse ratio be 1: 92,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 7) 33.4g, content 97.8%.The molecular formula of this compound: C
17H
15F
7O
3Molecular weight 400, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); (1.69 d, 1H); (2.44 m, 1H); (3.82 s, 3H); (5.30 s, 2H); (5.60 m, 1H); (5.80 m, 1H), specific rotation α=+ 33.4 degree.
Preparation Example 8:
Along inverse ratio be 2: 82,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 8)
According to the method in the Preparation Example 3, with the 1R-(Z)-3-(3 that along inverse ratio is 2: 8,3,3-three fluoro-1-propenyl)-2, (0.1mol is 2: 8 1R-3-aldehyde radical-2 by starting raw material along inverse ratio to 2-dimethyl cyclopropane carboxylic acid 20.8g, 2-dimethyl cyclopropane carboxylic acid methyl esters begins preparation), with 2,3,5, the reaction of 6-tetrafluoro-4-methoxyl group benzylalcohol 21.0g (0.1mol) obtain along inverse ratio be 2: 82,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 8) 33.7g, content 97.9%.The molecular formula of this compound: C
17H
15F
7O
3Molecular weight 400, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); (1.69 d, 1H); (2.44 m, 1H); (3.82 s, 3H); (5.30 s, 2H); (5.60 m, 1H); (5.80 m, 1H), specific rotation α=+ 33.4 degree.
Application Example 1
Add the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts and be shaped, then oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 1 in kerosene.
On this cover plate perfume base material, evenly spray the 4ml mentioned solution with micro-syringe, then at room temperature place and dried to obtain the disc type insecticidal incense I that a cover has 0.04w/w% the compounds of this invention 1 in 3 hours.
Similarly, the 0.4w/v% solution of preparation compound 2 in kerosene obtains the disc type insecticidal incense II that a cover has 0.04w/w% compound 2;
The 0.4w/v% solution of preparation compound 3 in kerosene obtains the disc type insecticidal incense III that a cover has 0.04w/w% compound 3;
The 0.4w/v% solution of preparation compound 4 in kerosene obtains the disc type insecticidal incense IV that a cover has 0.04w/w% compound 4;
The 0.4w/v% solution of preparation compound 6 in kerosene obtains the disc type insecticidal incense V that a cover has 0.04w/w% compound 4;
The 4w/v% solution of preparation esbiothrin in kerosene obtains the disc type insecticidal incense VI that a cover has the 0.4w/w% esbiothrin
The disc type insecticidal incense of I～VI is carried out kill mosquito evaluation of pesticide effectiveness contrast with reference to GB13917.4-92, and the examination worm is culex pipiens pollens, 2～3 days female mosquitos of not sucking blood after sprouting wings; 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, puts to fragrant frame, lights timing, removes mosquito-repellent incense behind the 1min, records at set intervals down and out examination mosquito number, and experimental result sees Table 1:
The comparison of table 1. the compounds of this invention and control compounds effect exterminating mosquito
| Insecticidal incense | Effective constituent | Concentration w/w% | KT50(min) |
| Insecticidal incense I | Compound 1 | 0.04 | 4.1 |
| Insecticidal incense II | Compound 2 | 0.04 | 6.2 |
| Insecticidal incense III | Compound 3 | 0.04 | 6.1 |
| Insecticidal incense IV | Compound 4 | 0.04 | 9.5 |
| Insecticidal incense V | Compound 6 | 0.04 | 3.9 |
| Insecticidal incense VI | Esbiothrin | 0.4 | 6.8 |
The result shows, compound 1R of the present invention, the compound 1 of Z configuration is (along 2 of inverse ratio 1: 1,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester) and compound 6 (2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, trans-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester) relative effectivenes is all at more than 2 times of dimefluthrin, and obviously is better than the isomeric compound 2,3 and 4 of other several configurations.
Application Example 2
Kerosene with 0.3 weight part compound 1 and 59.7 weight parts under heating mixes a kind of pesticide preparation of preparation.The preparation that obtains is put into inhalator jar, a valve is housed on the tank, and inject 40.0 weight parts the third butane adding to depress by this valve, to obtain a kind of insect aerosol, wherein contain compound 10.3w/w%.
This insect aerosol is carried out mosquito according to GB13917.2-92, fly, the efficacy testing of Groton bug adopts airtight drum device.Detailed process is as follows: will put into cylinder for the examination insect; after trying worm recovery normal activity; metered injection 1g medicament from the insect aerosol tank; extracting baffle plate behind the 1min out makes the examination worm contact with medicament; immediately timing, and begin record, record at regular intervals down and out examination borer population; to all be transferred in the dependent insect cage of cleaning for the examination worm behind the 20min, check dead examination borer population behind the 24h.Wherein Groton bug is checked the 72h mortality ratio.The results are shown in Table 2:
The insect aerosol of table 2. the compounds of this invention preparation is to mosquito, fly, the insect killing effect of Groton bug
| Insect | KT50 (mosquito/fly/cockroach) | 24 hours mortality ratio |
| Mosquito | 5.7 minute | 100％ |
| Fly | 4.9 minute | 100％ |
| Groton bug | 5.9 minute | 95％(72h) |
[0069]The result shows: the aerosol of the compounds of this invention 1 preparation is to mosquito, and fly, Groton bug have good insect killing effect.
Application Example 3: at the volatility preparation of room temperature use
Get the compounds of this invention 6 (2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, trans-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester) 1mg is dissolved in that prepared solution is distributed on the filter paper of a 20cm * 50cm in the 20ml acetone, and removes acetone by dry air and namely obtain a kind of volatility preparation.This volatility preparation is hung on edge on the doorway in room, invade without mosquito a night.
Claims (8)
1. pyrethroid compound, 2,3,5,6-tetrafluoro-4-methoxy-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2, the steric isomer of 2-dimethyl cyclopropane carboxylic acid ester is characterized in that: described compound structure is shown in (A) formula, the carbon-carbon double bond of carboxylic moiety is the Z configuration in the formula (A), and the absolute steric configuration of 1 of cyclopropane is the R configuration; Be that described compound is 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester
2. pyrethroid compound claimed in claim 1, it is characterized in that: the three-dimensional arrangement of described compound chrysanthemumic acid part triatomic ring is transconfiguration, be that described compound is 2,3,5,6-tetrafluoro-4-methoxy-benzyl-1R, trans-(Z)-3-(3,3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
3. a kind of synthetic method of pyrethroid compound claimed in claim 1, it is characterized in that: use suc as formula the 1R-(Z) shown in (B)-3-(3,3,3-, three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid and 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol is according to the mol ratio of 0.8 ~ 1.2:1, in organic solvent, under 60 ~ 130 ℃, sulfuric acid or Catalyzed by p-Toluenesulfonic Acid, carry out esterification and obtain; Wherein, the mol ratio of catalyst sulfuric acid or tosic acid and 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol is 0.01 ~ 0.1:1
4. the another kind of synthetic method of pyrethroid compound claimed in claim 1, it is characterized in that: by the 1R-(Z) shown in the formula (B)-3-(3,3,3-, three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid obtains 1R-(Z)-3-(3 through the chloride reagent chloride, 3,3-, three fluoro-1-propenyl)-2, behind the 2-dimethyl cyclopropane carboxylic acid acyl chlorides, again with 2,3,5,6-tetrafluoro-4-methoxyl group benzylalcohol reaction makes
5. claim 3 or 4 described any one synthetic methods is characterized in that: the compound shown in the formula (B) is by 1R-3-(3,3,3-, three fluoro-1-propenyl)-2, and 2-dimethyl cyclopropane carboxylic acid recrystallization separates and obtains; Wherein, the used solvent of recrystallization is methanol-water, methyl alcohol: the weight ratio of water is 0.1～10:1; 1R-3-(3,3,3-, three fluoro-1-propenyl)-2, the weight ratio of 2-dimethyl cyclopropane carboxylic acid and used recrystallization solvent is 0.05 ~ 0.1:1.
6. synthetic method claimed in claim 5, it is characterized in that: described 1R-3-(3,3,3-, three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid is by the aldehydo-ester shown in (C) formula and wittig reagent (C
6H
5)
3P
+-CH
2CF
3 -Mol ratio with 0.8～1.2:1 in tetrahydrofuran (THF) was reacted 5 ~ 20 hours under 0 ~ 40 ℃, and the compound that obtains formula (D) is hydrolyzed and obtains
(C) R=CH wherein
3, CH
2CH
3(D) R=CH wherein
3, CH
2CH
3
7. the application of pyrethroid compound claimed in claim 1 aspect the control sanitary insect pest, it is characterized in that: described sanitary insect pest is mosquito, fly or Groton bug.
8. application claimed in claim 7 is characterized in that: described compound is formed in disc type insecticidal incense, electric mosquito repellent tablet or electric liquid device under the heated volatile, or makes and be fit to the filter paper ribbon formulation that at normal temperatures volatilization is used.
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| CN109907067A (en) * | 2017-12-12 | 2019-06-21 | 江苏扬农化工股份有限公司 | It can be used for the ester compounds of desinsection |
| CN109988068A (en) * | 2017-12-29 | 2019-07-09 | 江苏扬农化工股份有限公司 | A kind of pyrethroid compound of single spatial configuration |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4370346A (en) * | 1979-12-21 | 1983-01-25 | Imperial Chemical Industries Plc | Halogenated esters |
| CN101381306A (en) * | 2008-10-14 | 2009-03-11 | 江苏扬农化工股份有限公司 | Pyrethroid compounds and application |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4370346A (en) * | 1979-12-21 | 1983-01-25 | Imperial Chemical Industries Plc | Halogenated esters |
| CN101381306A (en) * | 2008-10-14 | 2009-03-11 | 江苏扬农化工股份有限公司 | Pyrethroid compounds and application |
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| JP特开2002-249464 2002.09.06 |
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