CN101671251B - Pyrethroid compound as well as preparation method and application thereof - Google Patents
Pyrethroid compound as well as preparation method and application thereof Download PDFInfo
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- CN101671251B CN101671251B CN 200910142187 CN200910142187A CN101671251B CN 101671251 B CN101671251 B CN 101671251B CN 200910142187 CN200910142187 CN 200910142187 CN 200910142187 A CN200910142187 A CN 200910142187A CN 101671251 B CN101671251 B CN 101671251B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 79
- 239000002728 pyrethroid Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 38
- 241000238631 Hexapoda Species 0.000 claims abstract description 18
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 9
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims abstract description 5
- 230000000749 insecticidal effect Effects 0.000 claims description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 18
- 241000255925 Diptera Species 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- UYCSRVMHOHFVTN-UHFFFAOYSA-N 1-(2,3,5,6-tetrafluoro-4-methoxyphenyl)ethanol Chemical compound O(C)C1=C(C(=C(C(=C1F)F)C(O)C)F)F UYCSRVMHOHFVTN-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 9
- 238000001953 recrystallisation Methods 0.000 claims description 7
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000010189 synthetic method Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000000077 insect repellent Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 claims description 2
- 230000032050 esterification Effects 0.000 claims description 2
- 238000005886 esterification reaction Methods 0.000 claims description 2
- -1 under 60-130 °C Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 27
- 239000000243 solution Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 13
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 9
- 239000000443 aerosol Substances 0.000 description 7
- 239000003350 kerosene Substances 0.000 description 7
- 229940125904 compound 1 Drugs 0.000 description 6
- 229940125782 compound 2 Drugs 0.000 description 5
- 229940126214 compound 3 Drugs 0.000 description 5
- 230000000857 drug effect Effects 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 230000002147 killing effect Effects 0.000 description 4
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- 241000256113 Culicidae Species 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
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- ZCVAOQKBXKSDMS-PVAVHDDUSA-N (+)-trans-(S)-allethrin Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)O[C@@H]1C(C)=C(CC=C)C(=O)C1 ZCVAOQKBXKSDMS-PVAVHDDUSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
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- 230000004071 biological effect Effects 0.000 description 2
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- DYLIWHYUXAJDOJ-OWOJBTEDSA-N (e)-4-(6-aminopurin-9-yl)but-2-en-1-ol Chemical compound NC1=NC=NC2=C1N=CN2C\C=C\CO DYLIWHYUXAJDOJ-OWOJBTEDSA-N 0.000 description 1
- MMEAVAVRZYNYFB-UHFFFAOYSA-N 1,2-dimethylcyclopropane-1-carboxylic acid Chemical compound CC1CC1(C)C(O)=O MMEAVAVRZYNYFB-UHFFFAOYSA-N 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000256059 Culex pipiens Species 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a pyrethroid compound which is a stereoisomer of 2, 3, 5, 6- teflon-4-methoxymethyl benzyl-3-(3, 3, 3-trifluoro-1-propenyl)-2,2-dimethyl-cyclopropane carboxylic acid ester and is characterized in that the structure of the compound is shown as forma (A); the carbon-carbon double bond of the carboxylic acid part in the forma (A) is a Z configuration and the absolute three-dimensional configuration of the cyclopropane 1-bit is an R configuration; and the compound is the 2, 3, 5, 6-teflon-4-methoxymethyl benzyl-1R-(Z)-3-(3, 3, 3-trifluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester. The pyrethroid compound has very high activity and significant effect to control the sanitory insect pests. The invention also provides a preparation method and application thereof.
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 to prevent and treat mosquito, and has higher insecticidal activity, and this is widely known by the people.Because it has efficiently, low toxicity, low residue, environment compatibility are good, obtained application widely in the prevention and control field of sanitary insect pest.But growth along with duration of service, mosquitos and flies has produced certain resistance (Gao Xiwu etc. to some traditional pyrethroid products (as esbiothrin) etc., Chinese media biology and control magazine, 2004,15 (2), 105), the former dose of pyrethroid that needs to add in products such as mosquito-repellent incense or aerosol for prevention effect same before reaching has increased greatly.This has not only improved production cost, has also increased the weight of environmental pressure.
We by the structure of modification to traditional pyrethroid acid, alcohol moiety, have formed the fluorine-containing pyrethroid compound of a series of novelties in CN 101381306A.The preliminary test of pesticide effectiveness of these compounds shows to have excellent insecticidal activity, knocks down soon the lethality rate height.On the other hand; along with people are more and more higher to environmental protection requirement, 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 toxicity non-target organism, improve security, reduce the left drug environmental pollution.Based on such thinking, we are for the compound 2,3,5 preferably of activity wherein, 6-tetrafluoro-4-methoxyl methyl benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester has carried out more deep research, 2 unsymmetrical carbons are arranged on this compound cyclopropane, have isomer, and there is carbon-carbon double bond in carboxylic moiety, also has 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, confirmed 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester is a highly active isomer.Prevent and treat sanitary insect pest with it, not only do not have cross resistance, and, greatly reduce dosage, reduced use cost, also reduced environmental pressure because its basic activity is very high with before traditional pyrethroid products such as esbiothrin.
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, be 2,3,5,6-tetrafluoro-4-methoxyl methyl 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-methoxyl methyl 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) has cis-trans-isomer and exists because of the cyclopropane plane is asymmetric.Therefore, described pyrethroid compound can be that one of described cis-trans-isomer (both can be 2,3,5,6-tetrafluoro-4-methoxyl methyl 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-methoxyl methyl benzyl-1R, cis-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester), or these two kinds of isomer are with arbitrary proportion phase blended mixture.The caused drug effect difference of this isomery is not remarkable, and we discover 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 1R-(the Z)-3-(3 shown in (B), 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid and 2,3,5,6-tetrafluoro-4-methoxyl methyl benzylalcohol is according to 0.8～1.2: 1 mol ratio, in organic solvents such as toluene or hexanaphthene, under 60-130 ℃, sulfuric acid or Catalyzed by p-Toluenesulfonic Acid, carry out esterification and obtain; Wherein, catalyst sulfuric acid or tosic acid and 2,3,5, the mol ratio of 6-tetrafluoro-4-methoxyl methyl benzylalcohol is 0.01～0.1: 1.
The another kind of synthetic method of described pyrethroid compound is: by 1R-(the Z)-3-(3 shown in the formula (B), 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 methyl benzylalcohol reaction makes; Wherein, described chloride reagent can be a sulfur oxychloride.
Compound 1R-(the Z)-3-of described formula (B) (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 a 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 aldehydo-ester shown in (C) formula and wittig reagent (C
6H
5)
3P
+-CH
2CF
3 -In anhydrous organic solvents such as tetrahydrofuran (THF) with 0.8～1.2: 1 mol ratio is 0～40 ℃ of down reaction 5～20 hours, and the compound that obtains formula (D) hydrolysis again 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 hydrolysis or hydrolysis in sig water in diluted acid, 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 in the application of remove 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 remove killing mosquito, fly or Groton bug.
Because described pyrethroid compound has than the existing conventional higher vapour pressure of using of pyrethroid, therefore can be made into the various desinsection formulations under heated volatile, as disc type insecticidal incense, electric mosquito repellent tablet or electric liquid device etc., or make the filter paper ribbon formulation that is fit to volatilization use at normal temperatures.
Embodiment
Explain technical scheme of the present invention and effect in detail with the form of embodiment below, but the present invention is not limited to following examples.
Preparation embodiment 1:
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, dropping into along inverse ratio is 1: 1 1R-3-aldehyde radical-2,2-dimethyl cyclopropane carboxylic acid methyl esters 15.6g (0.1mol), and the 50ml anhydrous tetrahydro furan adds the 0.5g potassium tert.-butoxide again, drips 34.5g (0.1mol) (C while stirring under 5 ℃
6H
5)
3P
+-CH
2CF
3 -Be dissolved in the suspension liquid of 80ml tetrahydrofuran (THF), drip in 2 hours and finish, be warming up to 20 ℃ of reactions 8 hours then.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 and be heated to 80 ℃ of reactions 2 hours down, be cooled to room temperature, branch removes toluene layer.Water layer is transferred in the 250ml there-necked flask, and the ice-water bath insulation drips 30% sulphuric acid soln 100g down, 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, be heated to 100 ℃ under the negative pressure of air-dry back and 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 embodiment 2:
The suitable inverse ratio of preparation is 1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2 of 1: 1, 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 1: 1 weight ratio again stirred 30 minutes down at 40 ℃, filtered, the gained solid stirred 30 minutes down at 30 ℃ in the methanol-water solution that drops into 1: 2 weight ratio of 15g, filter once more, the gained solid again with the washing of 5ml clear water once promptly get the suitable inverse ratio of compound after air-dry and is 1R-(Z)-3-(3 of 1: 1,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 5.8g, content 98.7%.Merge 2 times filtering mother liquor, 40 ℃, being concentrated on thin-film evaporator under the 100mmHg negative pressure has just had solid to separate out, and fetches concentrated solution and is cooled to 5 ℃, has some solids to separate out again, filter, it is air-dry that to obtain along inverse ratio be 1R-(E)-3-(3,3,3-three fluoro-1-propenyl)-2 of 1: 1,2-dimethyl cyclopropane carboxylic acid 4.2g, content 95.1%.
Preparation embodiment 3:
Along inverse ratio be 1: 12,3,5,6-tetrafluoro-4-methoxyl methyl 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, the suitable inverse ratio that input prepares by embodiment 2 methods is 1R-(Z)-3-(3 of 1: 1,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol), 2,3,5,6-tetrafluoro-4-methoxyl methyl benzylalcohol 22.4g (0.1mol), 180ml toluene is loaded onto water trap, add the 0.1g tosic acid again, 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 of 100g 5% to wash once, and last 100g water washs once again, collect toluene layer under the 10mmHg negative pressure, be heated to 100 ℃ purify that solvent toluene obtains 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 1) 36.9g, content 98.3%, yield 90.7% is 1: 1 along inverse ratio.The molecular formula of this compound: C
18H
17F
7O
3Molecular weight 414, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); 1.69 (d, 1H); 2.44 (m, 1H); 3.40 (s, 3H); 4.59 (s, 2H); 5.30 (s, 2H); 5.60 (m, 1H); 5.80 (m, 1H), specific rotation α=+ 37.2 degree.
Preparation embodiment 4:
Control compounds along inverse ratio be 1: 12,3,5,6-tetrafluoro-4-methoxyl methyl 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 for preparing among the embodiment 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 methyl benzylalcohol 22.4g (0.1mol) reaction obtains 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R-(E)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 2) 35.8g, content 97.9%.The molecular formula of this compound: C
18H
17F
7O
3Molecular weight 414, 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); 3.41 (s, 3H); 4.59 (s, 2H); 5.27 (m, 2H); 5.79 (m, 1H); 6.03 (m, 1H), specific rotation α=+ 37.2 degree.
Preparation embodiment 5:
Control compounds along inverse ratio be 1: 12,3,5,6-tetrafluoro-4-methoxyl methyl 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-methoxyl methyl 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 for preparing among the embodiment 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)-2,2-dimethyl cyclopropane carboxylic acid; Obtain 1S-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2 respectively by embodiment 2 described method recrystallizations, 2-dimethyl cyclopropane carboxylic acid and 1S-(E)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid.
According to the method for preparing among the embodiment 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 methyl benzylalcohol reaction obtains 2,3,5,6-tetrafluoro-4-methoxyl methyl 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
18H
17F
7O
3Molecular weight 414, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); 1.69 (d, 1H); 2.44 (m, 1H); 3.40 (s, 3H); 4.59 (s, 2H); 5.30 (s, 2H); 5.60 (m, 1H); 5.80 (m, 1H), specific rotation α=-37.2 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 methyl benzylalcohol reaction obtains 2,3,5,6-tetrafluoro-4-methoxyl methyl 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
18H
17F
7O
3Molecular weight 414, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); 1.71 (d, 1H); 2.12 (m, 1H); 3.41 (s, 3H); 4.59 (s, 2H); 5.27 (m, 2H); 5.79 (m, 1H); 6.03 (m, 1H), specific rotation α=-37.2 degree.
Preparation embodiment 6:
2,3,5,6-tetrafluoro-4-methoxyl methyl 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 for preparing among the embodiment 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 methyl benzylalcohol 22.4g (0.1mol) reaction obtains 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R, cis-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 5) 34.9g, content 98.2%.The molecular formula of this compound: C
18H
17F
7O
3Molecular weight 414, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); 1.69 (d, 1H); 2.44 (m, 1H); 3.40 (s, 3H); 4.59 (s, 2H); 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=+ 37.2 degree.
Preparation embodiment 7:
2,3,5,6-tetrafluoro-4-methoxyl methyl 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 for preparing among the embodiment 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 methyl benzylalcohol 22.4g (0.1mol) reaction obtains 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R, cis-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 6) 35.2g, content 98.0%.The molecular formula of this compound: C
18H
17F
7O
3Molecular weight 414, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); 1.69 (d, 1H); 2.44 (m, 1H); 3.40 (s, 3H); 4.59 (s, 2H); 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=+ 37.2 degree.
Preparation embodiment 8:
Along inverse ratio be 1: 92,3,5,6-tetrafluoro-4-methoxyl methyl 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 for preparing among the embodiment 3, with the 1R that along inverse ratio is 1: 9,-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol, is 1: 9 1R-3-aldehyde radical-2 by starting raw material along inverse ratio, and 2-dimethyl cyclopropane carboxylic acid methyl esters begins preparation), with 2,3,5, the reaction of 6-tetrafluoro-4-methoxyl methyl benzylalcohol 22.4g (0.1mol) obtain along inverse ratio be 1: 92,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 7) 33.6g, content 98.2%.The molecular formula of this compound: C
18H
17F
7O
3Molecular weight 414, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); 1.69 (d, 1H); 2.44 (m, 1H); 3.40 (s, 3H); 4.59 (s, 2H); 5.30 (s, 2H); 5.60 (m, 1H); 5.80 (m, 1H), specific rotation α=+ 37.2 degree.
Preparation embodiment 9:
Along inverse ratio be 2: 82,3,5,6-tetrafluoro-4-methoxyl methyl 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 for preparing among the embodiment 3, with the 1R that along inverse ratio is 2: 8,-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol, is 2: 8 1R-3-aldehyde radical-2 by starting raw material along inverse ratio, and 2-dimethyl cyclopropane carboxylic acid methyl esters begins preparation), with 2,3,5, the reaction of 6-tetrafluoro-4-methoxyl methyl benzylalcohol 22.4g (0.1mol) obtain along inverse ratio be 2: 82,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound 8) 34.1g, content 98.4%.The molecular formula of this compound: C
18H
17F
7O
3Molecular weight 414, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.29 (m, 6H); 1.69 (d, 1H); 2.44 (m, 1H); 3.40 (s, 3H); 4.59 (s, 2H); 5.30 (s, 2H); 5.60 (m, 1H); 5.80 (m, 1H), specific rotation α=+ 37.2 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, oven dry forms plate-like insecticidal incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound 1 in kerosene.
On this cover incense coil base material, evenly spray the above-mentioned solution of 4ml, at room temperature place then and dried in 3 hours to obtain the disc type insecticidal incense I that a cover has 0.04w/w% The compounds of this invention 1 with micro-syringe.
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 0.4w/v% solution of preparation tetrafluoro in kerosene obtains the disc type insecticidal incense VI that a cover has 0.04w/w% tetrafluoro
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 a culex pipiens pollens, and the 2-3 days female mosquitos of not sucking blood in back sprout wings; Detailed process is to draw 20 examination mosquitos with mosquito sucking tube, 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, writes down down and out examination mosquito number at set intervals, 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 | 3.2 |
| Insecticidal incense | Effective constituent | Concentration w/w% | KT50(min) |
| Insecticidal incense II | Compound 2 | 0.04 | 5.2 |
| Insecticidal incense III | Compound 3 | 0.04 | 5.1 |
| Insecticidal incense IV | Compound 4 | 0.04 | 8.2 |
| Insecticidal incense V | Compound 6 | 0.04 | 3.1 |
| Insecticidal incense VI | Tetrafluoro | 0.04 | 7.6 |
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-methoxyl methyl 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-methoxyl methyl 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 tetrafluoro, 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 the aerosol jar, on jar a valve is housed, and inject 40.0 weight parts, third butane adding to depress,, wherein contain compound 10.3w/w% to obtain a kind of insect aerosol by this valve.
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 waiting to try worm recovery normal activity; metered injection 1g medicament from the insect aerosol jar; extracting baffle plate behind the 1min out makes the examination worm contact with medicament; down and out examination borer population is write down in timing immediately, and opening entry at regular intervals; to all be transferred in the dependent insect cage of cleaning behind the 20min, check dead examination borer population behind the 24h for the examination worm.Wherein Groton bug is checked the 72h mortality ratio.The results are shown in Table 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 | 4.8 minute | 100％ |
| Fly | 4.3 minute | 100％ |
| Groton bug | 6.2 minute | 90％(72h) |
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-methoxyl methyl 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 promptly obtain a kind of volatility preparation.This volatility preparation is hung on the upper edge, doorway in room, do not have mosquito a night and invade.
Claims (10)
1. pyrethroid compound, be 2,3,5,6-tetrafluoro-4-methoxyl methyl 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-methoxyl methyl benzyl-1R-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester
2. the described pyrethroid compound of claim 1, it is characterized in that: the three-dimensional arrangement of described compound chrysanthemumic acid part triatomic ring is a transconfiguration, be that described compound is 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R, trans-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
3. the described pyrethroid compound of claim 1, it is characterized in that: the three-dimensional arrangement of described compound chrysanthemumic acid part triatomic ring is a cis-configuration, be that described compound is 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R, cis-(Z)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
4. a kind of synthetic method of the described pyrethroid compound of claim 1, it is characterized in that: use suc as formula 1R-(the Z)-3-(3 shown in (B), 3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid and 2,3,5,6-tetrafluoro-4-methoxyl methyl benzylalcohol is according to 0.8～1.2: 1 mol ratio, in organic solvent, under 60-130 ℃, sulfuric acid or Catalyzed by p-Toluenesulfonic Acid, carry out esterification and obtain; Wherein, catalyst sulfuric acid or tosic acid and 2,3,5, the mol ratio of 6-tetrafluoro-4-methoxyl methyl benzylalcohol is 0.01～0.1: 1
。
5. the another kind of synthetic method of the described pyrethroid compound of claim 1, it is characterized in that: by 1R-(the Z)-3-shown in the formula (B) (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 methyl benzylalcohol reaction makes
6. claim 4 or 5 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 a 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.
7. the described synthetic method of claim 6, it is characterized in that: described 1R-3-(3,3,3-three fluoro-1-propenyl)-2, the 2-dimethyl cyclopropane carboxylic acid is by aldehydo-ester shown in (C) formula and wittig reagent (C
6H
5)
3P
+-CH
2CF
3 -In tetrahydrofuran (THF) with 0.8～1.2: 1 mol ratio is 0～40 ℃ of down reaction 5～20 hours, and the compound that obtains formula (D) hydrolysis again obtains
(C) R=CH wherein
3, CH
2CH
3(D) R=CH wherein
3, CH
2CH
3
8. the application of the described pyrethroid compound of claim 1 aspect the control sanitary insect pest.
9. the described application of claim 8 is characterized in that: described sanitary insect pest is mosquito, fly or Groton bug.
10. the described application of claim 8 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 volatilization is at normal temperatures used.
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| CN 200910142187 CN101671251B (en) | 2009-05-21 | 2009-06-05 | Pyrethroid compound as well as preparation method and application thereof |
| PCT/CN2010/070669 WO2010133098A1 (en) | 2009-05-21 | 2010-02-11 | Pyrethroid compound, preparation process and use thereof |
| MYPI2011005082A MY159352A (en) | 2009-05-21 | 2010-02-11 | Pyrethroid compound, preparation process and use thereof |
| JP2012511126A JP2012527409A (en) | 2009-05-21 | 2010-02-11 | Pyrethroid compound, production method and use thereof |
| SG2011077062A SG175295A1 (en) | 2009-05-21 | 2010-02-11 | Pyrethroid compound, preparation process and use thereof |
| US13/259,275 US8629296B2 (en) | 2009-05-21 | 2010-02-11 | Pyrethroid compound, preparation process and use thereof |
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| CN101971857A (en) * | 2010-10-18 | 2011-02-16 | 江苏扬农化工股份有限公司 | Injurious insect repellent powder and application thereof |
| CN102030691A (en) * | 2010-11-22 | 2011-04-27 | 中山凯中有限公司 | Fluorine-contained cyclopropane carboxylic ether compound as well as preparation method and application thereof |
| CN104649908B (en) * | 2013-11-18 | 2016-08-24 | 江苏扬农化工股份有限公司 | A kind of pyrethroid compound of single spatial configuration and its preparation method and application |
| CN105379750A (en) * | 2015-10-14 | 2016-03-09 | 王芬明 | Pesticidal composition, preparation containing same 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 |
| CN109988068A (en) * | 2017-12-29 | 2019-07-09 | 江苏扬农化工股份有限公司 | A kind of pyrethroid compound of single spatial configuration |
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