CN101492393B - Pyrethroid compounds, preparation and use thereof - Google Patents
Pyrethroid compounds, preparation and use thereof Download PDFInfo
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- CN101492393B CN101492393B CN 200910118875 CN200910118875A CN101492393B CN 101492393 B CN101492393 B CN 101492393B CN 200910118875 CN200910118875 CN 200910118875 CN 200910118875 A CN200910118875 A CN 200910118875A CN 101492393 B CN101492393 B CN 101492393B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 44
- 239000002728 pyrethroid Substances 0.000 title abstract description 12
- 241000255925 Diptera Species 0.000 claims abstract description 36
- 241000238631 Hexapoda Species 0.000 claims abstract description 32
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 16
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 10
- -1 chrysanthemumic acid acyl chlorides Chemical class 0.000 claims description 10
- XLOPRKKSAJMMEW-UHFFFAOYSA-N chrysanthemic acid Chemical compound CC(C)=CC1C(C(O)=O)C1(C)C XLOPRKKSAJMMEW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003814 drug Substances 0.000 claims description 8
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 8
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 claims description 8
- 230000032050 esterification Effects 0.000 claims description 6
- 238000005886 esterification reaction Methods 0.000 claims description 6
- 230000002147 killing effect Effects 0.000 claims description 6
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- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims 3
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- JDICMOLUAHZVDS-UHFFFAOYSA-N 4-fluoro-3-phenoxybenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1OC1=CC=CC=C1 JDICMOLUAHZVDS-UHFFFAOYSA-N 0.000 description 2
- 241000256059 Culex pipiens Species 0.000 description 2
- 241000256057 Culex quinquefasciatus Species 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
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- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 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 1
- KGANAERDZBAECK-UHFFFAOYSA-N (3-phenoxyphenyl)methanol Chemical compound OCC1=CC=CC(OC=2C=CC=CC=2)=C1 KGANAERDZBAECK-UHFFFAOYSA-N 0.000 description 1
- UFXDRIJUGWOQTP-UHFFFAOYSA-N (4-fluoro-3-phenoxyphenyl)methanol Chemical compound OCC1=CC=C(F)C(OC=2C=CC=CC=2)=C1 UFXDRIJUGWOQTP-UHFFFAOYSA-N 0.000 description 1
- 241001674044 Blattodea Species 0.000 description 1
- 0 CC(C)([C@@]1C=CC(F)(F)F)C1C(OC(*)c(cc1)cc(Oc2ccccc2)c1F)=O Chemical compound CC(C)([C@@]1C=CC(F)(F)F)C1C(OC(*)c(cc1)cc(Oc2ccccc2)c1F)=O 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
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- ROVGZAWFACYCSP-MQBLHHJJSA-N [2-methyl-4-oxo-3-[(2z)-penta-2,4-dienyl]cyclopent-2-en-1-yl] (1r,3r)-2,2-dimethyl-3-(2-methylprop-1-enyl)cyclopropane-1-carboxylate Chemical compound CC1(C)[C@H](C=C(C)C)[C@H]1C(=O)OC1C(C)=C(C\C=C/C=C)C(=O)C1 ROVGZAWFACYCSP-MQBLHHJJSA-N 0.000 description 1
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- 230000001442 anti-mosquito Effects 0.000 description 1
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- BECPQYXYKAMYBN-UHFFFAOYSA-N casein, tech. Chemical compound NCCCCC(C(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(CC(C)C)N=C(O)C(CCC(O)=O)N=C(O)C(CC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(C(C)O)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=N)N=C(O)C(CCC(O)=O)N=C(O)C(CCC(O)=O)N=C(O)C(COP(O)(O)=O)N=C(O)C(CCC(O)=N)N=C(O)C(N)CC1=CC=CC=C1 BECPQYXYKAMYBN-UHFFFAOYSA-N 0.000 description 1
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- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to pyrethroid compounds with general formula of (A), or stereochemical isomers thereof, or a mixture of the stereochemical isomers and a preparation method of the compounds and the application thereof in hygiene insecticidal products. In the formula (A), R refers to F atom or H atom, and Z is cyano (-CN) or H atom. Experiments show that the compounds have good effects on preventing sanitary insect pests of mosquitoes, flies, German cockroaches, etc.
Description
Technical field
The present invention relates to pyrethroid compound, relate in particular to a kind of compound that meets following formula (A), or its three-dimensional chemical isomer, or the mixture of these steric isomers with and preparation method thereof with the application in control sanitary insect pest field.
(in formula: R is F atom or H atom, Z be cyano group (CN) or the H atom.)
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.But the growth along with duration of service, mosquitos and flies has produced certain resistance (Ghosh force 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 the 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.
The present invention has formed the fluorine-containing pyrethroid compound of series of novel by the structure of modification to traditional pyrethroid acid, alcohol moiety.The preliminary test of pesticide effectiveness of these compounds shows to have good insecticidal activity, knocks down soon, and lethality rate is high, and the vapour pressure height can be stablized at normal temperatures and continue volatilization, is fit to production health pesticide preparation product.Due to the introducing of fluorine element, also greatly reduce the resistance risk of insect simultaneously.
Summary of the invention
Purpose of the present invention just is to provide a kind of pyrethroid compound of novelty, and the application on the sanitary insect pests such as control mosquito, fly, Groton bug.The objective of the invention is to be achieved through the following technical solutions:
The pyrethroid compound that provides with general formula (A):
Wherein: R is F atom or H atom, Z be cyano group (CN) or the H atom.
Work as R=F, Z=-CN is compound (1): alpha-cyano-3-phenoxy group-4-fluoro-benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound;
Work as R=H, Z=-CN is compound (2): alpha-cyano-3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound;
Work as R=F, Z=H is compound (3): 3-phenoxy group-4-fluoro-benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound;
Work as R=H, Z=H is compound (4): 3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound.
When R1 is R=F, Z=-CN and chrysanthemumic acid are compound alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2 during partly for the trans individual isomer of dextrorotation, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound; When R1 is R=H, Z=-CN and chrysanthemumic acid are compound alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2 during partly for the trans individual isomer of dextrorotation, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound.
Compound of the present invention comprises pyrethroid compound or its three-dimensional chemical isomer that provides with general formula (A), or the mixture of these steric isomers.
The preparation method that the present invention also provides described structure to satisfy the compound of formula (A), with reference to CN1303846A, the preparation method of chrysanthemum ester compound in CN101100445A, the compounds of this invention (A) can be prepared by following steps:
Be the chrysanthemumic acid acyl chlorides of (X) and structural formula for the pure direct esterification of (Y) or preparation are the aldehyde esterification preparation under NaCN exists for (Z) of the chrysanthemumic acid acyl chlorides of (X) and structural formula with structural formula with structural formula, in formula, the definition of R is the same.
Esterification can be carried out at organic solvents such as toluene, dimethylbenzene, hexanaphthenes, and the mol ratio of chrysanthemumic acid acyl chlorides and alcohol or aldehyde is 0.8: 1-1.5: 1, and the mol ratio of aldehyde and NaCN is 1: 1, adds pyridine as acid binding agent in reaction, temperature of reaction 0-25 ℃.
The present invention also provides described compound except the application of killing aspect the sanitary insect pests such as mosquito, fly or Groton bug.
The above-mentioned application of described compound be with described compound (A) as former medicine, be prepared into various forms of sterilants, be used for except killing mosquito, fly or Groton bug.
Described various forms of sterilant comprises disc type insecticidal incense, electric mosquito repellent tablet, electric liquid device or insect aerosol etc.
Below described structure is satisfied (A) the compounds of this invention be that the application of former medicine in preparation various forms sterilant is described in detail:
(1) preparation disc type insecticidal incense
Described disc type insecticidal incense is mixed with compound of the present invention to join after liquid form and makes in base material, and wherein the content of the compounds of this invention is 0.005-3.0w/w%.
The liquid form that compound of the present invention is mixed with is missible oil or the solution take kerosene as solvent.
Described missible oil can be sprayed onto on base material (fragrant base), forms the disc type insecticidal incense of the compounds of this invention that contains above-mentioned concentration, then oven dry.Also contain tensio-active agent and other auxiliary agents in described missible oil; The example of described tensio-active agent comprises one or more mixtures in alkyl-sulphate, alkylsulfonate, alkylaryl sulphonate, polyoxyalkylene alkyl, polyoxyalkylene alkyl aryl ether, polyoxyalkylene styryl phenyl ether, polyol ethers or sugar alcohol derivant; The example of described other auxiliary agents comprises one or more the mixture in perfume compound, tinting material or sterilant.
The base material of described disc type insecticidal incense is comprised of one or more inflammable substances and one or more tackiness agents, and wherein the weight ratio of inflammable substance and tackiness agent is 90: 10 to 99.9: 0.1.The example of inflammable substance comprises the plant drymeal that is selected from wood powder, pyrethrum extraction powder, citrus peel meal, palm oil-bound distemper, coconut shell powder or walnut parting, or is selected from the carbon dust of wood charcoal powder, activity charcoal powder or coal dust, or their mixture; The example of tackiness agent comprises the polymkeric substance of starch, casein, methylcellulose gum, carboxymethyl cellulose or polyvinyl alcohol of being selected from tapioca (flour), W-Gum or wheat starch and composition thereof.
Described disc type insecticidal incense base material normally by mixing inflammable substance and tackiness agent, is mediated with water, moulding and oven dry preparation.The shape of coiled mosquito-repellent incense base material is restriction not, can be plate-like or strip.The present invention uses diameter 12cm and thickness to be the conventional coil shape base material of 3-5mm in two line spices of a cover usually.
The disc type insecticidal incense that more than obtains can ordinary method be used.That is, light disc type insecticidal incense of the present invention in the habitat of insect near (for example dwelling house, office, stock barn) or its.The burning of disc type insecticidal incense can make the ester cpds volatilization of formula (A), after airborne effective constituent reaches certain concentration, to mosquito, fly, the sanitary insect pests such as Groton bug produce to be stimulated, drives, benumbs, knocks down and lethal effect, thereby reach mosquito, fly, the control of the sanitary insect pests such as Groton bug.
(2) preparation electric mosquito repellent tablet
Described electric mosquito repellent tablet is will contain the solution dropping of the compounds of this invention and/or be coated on the porosity base material to make, and in described anti-mosquito incense sheet, the content of the compounds of this invention is the 0.1-20mg/ sheet.Also contain the additive that is selected from antioxidant, stifling conditioning agent, spices or dyestuff in the described solution that contains compound (A).
The example of the porous substrate of described electric mosquito repellent tablet comprises paper pulp, asbestos, synthetic porous resin, porous, inorganic powder, glass fibre, sulphur thing powder or porous porcelain material; Described porous substrate is long 30-35mm, wide 20-22mm, the sheet of thick 1.5-2mm.An example that is used for porous pad of the present invention is the sheet that contains the paper pulp fiber of the cotton fibre of 50% weight and 50% weight, from absorptivity with keep the viewpoint of insecticidal active ingredient, preferably uses the natural fiber material film-making.
When using electric mosquito repellent tablet of the present invention in the habitat of insect near (for example dwelling house, office, stock barn) or its, controls certain temperature by electric heating panel, waving that the medicine that floods in sheet just begins to blow slowly is loose.After the effective constituent in space reaches certain concentration, just can be to mosquito, fly, the sanitary insect pests such as Groton bug produce to be stimulated, drives, benumbs, knocks down and lethal effect, thereby reaches mosquito, fly, the control of the sanitary insect pests such as Groton bug.
(3) preparation electric liquid device
Described electric liquid device is that the compounds of this invention is dissolved in aliphatic hydrocarbon, then adds the antioxidant of 0.1-0.5%, and 0.1-1% spices is mixed with the solution that contains 0.1-2% compound of the present invention and obtains; The aliphatic hydrocarbon of the preferred C14 component of described aliphatic hydrocarbon.
Electric liquid device liquid is by the wicking action of plug, mosquito-repellent incense liquid is taken to the top of plug from the bottom of plug, under the electrically heated effect of ring heater, after making the effective constituent in space reach certain concentration, just can be to mosquito, fly, the sanitary insect pests such as Groton bug produce to be stimulated, drives, benumbs, knocks down and lethal effect, thereby reach mosquito, fly, the control of the sanitary insect pests such as Groton bug.
(4) preparation insect aerosol
Described insect aerosol is that the composition that compound of the present invention, kerosene and synergistic agent, perfume compound, the sterilant according to circumstances selected mix under room temperature or heating condition is added in a tank that a valve is housed, and adding propelling agent to make by this valve in tank under pressure, in final composition, the content of the compounds of this invention is 0.001-0.5w/w%; Described propelling agent accounts for the 20-60% of composition total weight; Preferred liquefied petroleum gas (LPG), the third butane, dme or pressurized air, further preferred the third butane.
When insect aerosol of the present invention is used in the habitat of insect, by-pass valve control is opened, under the pressure-acting of propelling agent, produce high velocity air, tank is included the liquid aerosol dispersion of effective constituent and the gasification of propelling agent, the small liquid pearl that contains effective insecticidal constituent of formation is suspended in air, with mosquito, fly, the sanitary insect pests such as Groton bug contact, and reach the purpose of quick kill pests.
Based on above-mentioned achievement in research, the present invention proposes compound of the present invention and killing mosquito, fly, the application of the sanitary insect pest such as Groton bug aspect, and concrete application mode has been proposed.Through experiment, proved compound of the present invention and take its various sterilants as former medicine preparation, housefly, culex pipiens pollens, Groton bug etc. have been had significant prevention effect.
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: compound (1) alpha-cyano-3-phenoxy group-4-fluoro-benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 4-fluoro-3-phenoxy benzaldehyde 10.8g (0.05mol), pyridine 5g, be dissolved in the 80ml hexanaphthene, be added dropwise to the saturated aqueous solution that contains 2.45g (0.05mol) NaCN, throw to finish stir 10min, 10-20 ℃ slowly drips 2 in lower 2 hours, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purify solvent, obtain compound alpha-cyano-3-phenoxy group-4-fluoro-benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 20.2, content 94.3%, yield 88.1% (in aldehyde).The molecular formula of this compound: C
23H
18F
4NO
3, molecular weight: 432.4, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 5.93 (m, 1H); (5.70 m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); (6.25 s, 1H, benzyl α H); (6.83-6.89 m, 3H); (6.92-7.22 m, 5H).
Preparation Example 2: compound (2) alpha-cyano-3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 3-phenoxy benzaldehyde 9.9g (0.05mol), pyridine 5g, be dissolved in the 80ml hexanaphthene, be added dropwise to the saturated aqueous solution that contains 2.45g (0.05mol) NaCN, then add the 0.5g Tetrabutyl amonium bromide, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purify solvent, obtain compound alpha-cyano-3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 19.85, content 95.2%, yield 90.0% (in aldehyde).The molecular formula of this compound: C
23H
19F
3NO
3, molecular weight: 414.4, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 5.93 (m, 1H); (5.70 m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); (6.25 s, 1H, benzyl α H); (6.85-7.15 m, 4H); (6.92-7.22 m, 5H).
Preparation Example 3: compound (3) 3-phenoxy group-4-fluoro-benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 4-fluoro-3-phenoxy benzenemethanol 10.9g (0.05mol), pyridine 5g, be dissolved in 80ml toluene, throw to finish and stir, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purify solvent toluene, obtain compound 3-phenoxy group-4-fluoro-benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 18.82, content 96.9%, yield 89.9% (in aldehyde).The molecular formula of this compound: C
22H
20F
4O
3, molecular weight: 408.3, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 5.93 (m, 1H); (5.70 m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); (5.34 s, 2H, benzyl α H); (6.83-6.89 m, 3H); (6.92-7.22 m, 5H).
Preparation Example 4: compound (4) 3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 3-phenoxy benzenemethanol 10.2g (0.05mol), pyridine 5g, be dissolved in 80ml toluene, throw to finish and stir, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purify solvent toluene, obtain compound 3-phenoxy benzyl-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 18.45, content 97.3%, yield 91.9% (in aldehyde).The molecular formula of this compound: C
22H
21F
3O
3, molecular weight: 390.4, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 5.93 (m, 1H); (5.70 m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); (5.34 s, 2H, benzyl α H); (6.85-7.15 m, 4H); (6.92-7.22 m, 5H).
Preparation Example 5: compound (5) alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 4-fluoro-3-phenoxy benzaldehyde 10.8g (0.05mol), pyridine 5g, be dissolved in the 80ml hexanaphthene, be added dropwise to the saturated aqueous solution that contains 2.45g (0.05mol) NaCN, throw to finish and stir 10min, 10-20 ℃ slowly drips (1R in lower 2 hours, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purify solvent, obtain compound alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 19.9, content 94.9%, yield 88.3% (in aldehyde).The molecular formula of this compound: C
23H
18F
4NO
3, molecular weight: 432.4, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 5.93 (m, 1H); (5.70 m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); (6.25 s, 1H, benzyl α H); (6.83-6.89 m, 3H); (6.92-7.22 m, 5H), ee value 90%.
Preparation Example 6: compound (6) alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound synthetic
In the four-hole bottle of a 200ml, drop into 3-phenoxy benzaldehyde 9.9g (0.05mol), pyridine 5g is dissolved in the 80ml hexanaphthene, is added dropwise to the saturated aqueous solution that contains 2.45g (0.05mol) NaCN, add again the 0.5g Tetrabutyl amonium bromide, throw to finish stir 10min, 10-20 ℃ slowly drips (1R, 3S)-2 in lower 2 hours, 2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropane dicarbonyl chloride 13.6g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml 5% sodium hydroxide solution, 5% hydrochloric acid and saturated aqueous common salt once, divide oil-yielding stratum to be heated to 100 ℃ under the 10mmHg negative pressure and purify solvent, obtain compound alpha-cyano-3-phenoxy benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound 19.33, content 94.8%, yield 89.2% (in aldehyde).The molecular formula of this compound: C
23H
19F
3NO
3, molecular weight: 414.4, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 5.93 (m, 1H); (5.70 m, 1H) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); (6.25 s, 1H, benzyl α H); (6.85-7.15 m, 4H); (6.92-7.22 m, 5H), ee value 90%.
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 to 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 0.8w/v% solution of preparation compound (1) in kerosene.
Evenly drip the 5ml mentioned solution with micro-syringe on this cover plate perfume base material, then at room temperature place the disc type insecticidal incense I that had 0.04w/w% compound (1) in 3 hours to obtain a cover.
Application Example 2
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 to 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 0.8w/v% solution of preparation compound (2) in kerosene.
Evenly drip the 5ml mentioned solution with micro-syringe on this cover plate perfume base material, then at room temperature place the disc type insecticidal incense II that had 0.04w/w% compound (2) in 3 hours to obtain a cover.
Application Example 3
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 to 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 0.8w/v% solution of preparation compound (3) in kerosene.
Evenly drip the 5ml mentioned solution with micro-syringe on this cover plate perfume base material, then at room temperature place the disc type insecticidal incense III that had 0.04w/w% compound (3) in 3 hours to obtain a cover.
Application Example 4
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 to 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 0.8w/v% solution of preparation compound (4) in kerosene.
Evenly drip the 5ml mentioned solution with micro-syringe on this cover plate perfume base material, then at room temperature place the disc type insecticidal incense IV that had 0.04w/w% compound (4) in 3 hours to obtain a cover.
Application Example 5
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 to 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 0.8w/v% solution of preparation compound (5) in kerosene.
Evenly drip the 5ml mentioned solution with micro-syringe on this cover plate perfume base material, then at room temperature place the disc type insecticidal incense V that had 0.04w/w% compound (5) in 3 hours to obtain a cover.
Application Example 6
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 to 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 0.8w/v% solution of preparation compound (6) in kerosene.
Evenly drip the 5ml mentioned solution with micro-syringe on this cover plate perfume base material, then at room temperature place the disc type insecticidal incense VI that had 0.04w/w% compound (6) in 3 hours to obtain a cover.
Reference 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 to 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 0.8w/v% solution of preparation dimefluthrin in kerosene.
Evenly drip the 5ml mentioned solution with micro-syringe on this cover plate perfume base material, then at room temperature place the disc type insecticidal incense VII that had the 0.04w/w% dimefluthrin in 3 hours to obtain a cover.
Give birth to and survey embodiment 1
With Application Example 1-6, the disc type insecticidal incense of reference example 1 is carried out kill mosquito evaluation of pesticide effectiveness contrast according 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, put into airtight drum test set, appoint and get one section of tested mosquito-repellent incense, put to fragrant frame, light timing, remove mosquito-repellent incense after 1min, record at set intervals down and out examination mosquito number, to all be transferred in the dependent insect cage of cleaning for the examination mosquito after 20min, check dead examination mosquito number after 24h.
Experimental result sees Table 1:
The comparison of table 1. the compounds of this invention and control compounds effect exterminating mosquito
| Mosquito-repellent incense | Effective constituent | Concentration w/w% | KT50(min) | 24h mortality ratio (%) |
| Mosquito-repellent incense I | Compound (1) | 0.04 | 6.65 | 100 |
| Mosquito-repellent incense II | Compound (2) | 0.04 | 8.55 | 90 |
| Mosquito-repellent incense III | Compound (3) | 0.04 | 10.25 | 80 |
| Mosquito-repellent incense IV | Compound (4) | 0.04 | 12.33 | 75 |
| Mosquito-repellent incense V | Compound (5) | 0.04 | 5.03 | 100 |
| Mosquito-repellent incense VI | Compound (6) | 0.04 | 8.12 | 95 |
| Mosquito-repellent incense VII | Dimefluthrin | 0.04 | 8.47 | 95 |
The result demonstration, the relative effectivenes of compound (1) is at 1.3 times of dimefluthrin, and the relative effectivenes of the compound of individual isomer (5) is more at more than 1.8 times of dimefluthrin.
Application Example 7
With containing 1mg compound (1), 15mg BHT (2, the 6-di-tert-butyl-4-methy phenol) and the long 35mm of the preparation of 0.5mg dyestuff dipping, wide 22mm, the porous pad of thick 2mm (cotton fibre: 50% weight percent, paper pulp fiber: 50% weight percent), placed 3 days under room temperature, make electric mosquito repellent tablet.
Application Example 8
With containing 1mg compound (5), 15mg BHT (2, the 6-di-tert-butyl-4-methy phenol) and the long 35mm of the preparation of 0.5mg dyestuff dipping, wide 22mm, the porous pad of thick 2mm (cotton fibre: 50% weight percent, paper pulp fiber: 50% weight percent), placed 3 days under room temperature, make electric mosquito repellent tablet.
Reference example 2
With containing the 1mg dimefluthrin, 15mg BHT (2, the 6-di-tert-butyl-4-methy phenol) and the long 35mm of the preparation of 0.5mg dyestuff dipping, wide 22mm, the porous pad of thick 2mm (cotton fibre: 50% weight percent, paper pulp fiber: 50% weight percent), placed 3 days under room temperature, make electric mosquito repellent tablet.
Give birth to and survey embodiment 2
With Application Example 7 of the present invention, 8, reach reference example 2 and carry out the evaluation of pesticide effectiveness of mosquito is contrasted according to GB13917.5-92, adopt airtight drum device.Detailed process is as follows.With electric mosquito repellent tablet sample energising preheating 1h, 2h, 4h, 6h, 8h draws 20 female culex pipiens fatigans with mosquito sucking tube, puts into airtight drum test set, accurately smoked kill 1min, clock simultaneously, cut off the electricity supply after smoking, and remove the electric mosquito repellent sheet devices, record at regular intervals down and out examination mosquito number.The results are shown in Table 2:
The electric mat of table 2. the compounds of this invention preparation and the comparison of dimefluthrin electric mat effect
Result shows: the electric mat relative effectivenes take the compounds of this invention (1) as former medicine preparation is at 1.3 times of dimefluthrin, and the relative effectivenes of the compound of individual isomer (5) is more at more than 1.8 times of dimefluthrin.
Application Example 9
With 0.2 part of compound (1) and 0.3 part of BHT, the spices of 0.3 part, the n-tetradecane of 99.2 parts are combined and are prepared into mosquito liquid under heating.Then can becomes electric liquid device, wherein contains compound (1) 0.2w/w%.
Give birth to and survey embodiment 3
Application Example 9 of the present invention is carried out evaluation of pesticide effectiveness contrast according to GB13917.6-92, adopt airtight drum device.Detailed process is as follows: with electric liquid device sample energising 2h, 36h, 84h, 168h, 336h, draw 20 female culex pipiens fatigans with mosquito sucking tube, put into airtight drum test set, accurately smoked kill 1min, clock simultaneously, cut off the electricity supply after smoked, and remove the electric liquid device device, record at regular intervals down and out examination mosquito number.The results are shown in Table 3:
The vaporizer mosquito liquid insecticidal effect statistics of table 3. the compounds of this invention preparation
Result shows: the electric liquid device of the compounds of this invention (1) preparation has good prevention effect to mosquito
Application Example 10
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 tank, and inject 40.0 weight part the third butane adding to depress by this valve, to obtain a kind of insect aerosol, wherein contain compound (1) 0.3w/w%.
Give birth to and survey embodiment 4
Application Example 10 of the present invention 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 insect aerosol tank of the present invention; extracting baffle plate after 1min out makes the examination worm contact with medicament; timing immediately, 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 after 20min, check dead examination borer population after 24h.Wherein Groton bug is checked the 72h mortality ratio.The results are shown in Table 4:
The insect aerosol of table 4. 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 | 6.22 minute | 100％ |
| Fly | 7.58 minute | 100％ |
| Groton bug | 5.96 minute | 100％(72h) |
Result shows: the aerosol of the compounds of this invention (1) preparation is to mosquito, and fly, Groton bug have good insect killing effect.
Claims (4)
1. compound that meets following formula (A):
Wherein: R=F, Z=-CN, and the chrysanthemumic acid of this compound is partly trans for dextrorotation, and this compound is alpha-cyano-3-phenoxy group-4-fluoro-benzyl-(1R, 3S)-2,2-dimethyl-3-(2-trifluoromethyl vinyl) cyclopropanecarboxylcompound.
2. the preparation method of the compound of a kind of formula claimed in claim 1 (A) is characterized in that and can be prepared by following steps:
Be the chrysanthemumic acid acyl chlorides of (X) and structural formula for the pure direct esterification of (Y) or preparation are the aldehyde esterification preparation under NaCN exists for (Z) of the chrysanthemumic acid acyl chlorides of (X) and structural formula with structural formula with structural formula, in formula, R is the F atom;
Esterification can be carried out in toluene, dimethylbenzene or hexanaphthene, and the mol ratio of chrysanthemumic acid acyl chlorides and alcohol or aldehyde is 0.8:1-1.5:1, and the mol ratio of aldehyde and NaCN is 1:1, adds pyridine as acid binding agent in reaction, temperature of reaction 0-25 ℃.
3. a kind of application of compound aspect the control sanitary insect pest that meets formula (A) claimed in claim 1; Described sanitary insect pest is mosquito, fly or Groton bug.
4. application as claimed in claim 3 is characterized in that: the compound that satisfies (A) formula with described structure is prepared into various forms of sterilants as former medicine, is used for except killing mosquito, fly or Groton bug.
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Citations (3)
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|---|---|---|---|---|
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| US4379163A (en) * | 1978-02-28 | 1983-04-05 | Montedison, S.P.A. | Pyrethroids |
| CN101100445A (en) * | 2007-08-03 | 2008-01-09 | 华东师范大学 | Monohalogenated pyrethric acid alpha-cyano-4-fluoro-3-phenoxybenzyl ester and its preparation method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4379163A (en) * | 1978-02-28 | 1983-04-05 | Montedison, S.P.A. | Pyrethroids |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| CN101100445A (en) * | 2007-08-03 | 2008-01-09 | 华东师范大学 | Monohalogenated pyrethric acid alpha-cyano-4-fluoro-3-phenoxybenzyl ester and its preparation method and use |
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| CAS.RN 344776-03-0.《REGISTRY》.2001,1. * |
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