CN101735104B - Pyrethroid compound and application thereof - Google Patents
Pyrethroid compound and application thereof Download PDFInfo
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- CN101735104B CN101735104B CN 200810181007 CN200810181007A CN101735104B CN 101735104 B CN101735104 B CN 101735104B CN 200810181007 CN200810181007 CN 200810181007 CN 200810181007 A CN200810181007 A CN 200810181007A CN 101735104 B CN101735104 B CN 101735104B
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- dimethyl
- tetrafluoro
- cyclopropanecarboxylcompound
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- 239000002728 pyrethroid Substances 0.000 title claims abstract description 22
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 18
- 125000001246 bromo group Chemical group Br* 0.000 claims abstract description 8
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 8
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 8
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 claims abstract description 6
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims abstract description 4
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Landscapes
- Agricultural Chemicals And Associated Chemicals (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to pyrethroid compound, the preparation method thereof and the application thereof to the prevention and treatment of sanitary insects such as mosquitoes, flies, or cockroaches. The pyrethroid compound has the general formula of (A), wherein R is H atom, methyl or methoxymethyl (-CH2OCH3), X1 and X2 are same methyls, F atoms, Cl atoms or Br atoms, or X1 is trifluoromethyl-CF3 and X2 is F atom, Cl atom, Br atom or H atom. Experiments show that the pyrethroid compound which has the general formula of (A) has the good effect of preventing and treating the sanitary insects such as the mosquitoes, the flies, or the German cockroaches.
Description
Technical field
The present invention relates to a kind of pyrethroid compound, and preparation method and the application aspect the sanitary insect pests such as control mosquito, fly, cockroach thereof.
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 inventor 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, 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:
It is the pyrethroid compound of formula (A) that structural formula is provided, and (A) is as follows for formula:
Wherein R is H atom, methyl or methoxy methyl (CH
2OCH
3), X1, X2 are identical methyl, F atom, Cl atom or Br atom, perhaps X1 is trifluoromethyl (CF
3), X2 is F atom, Cl atom, Br atom or H atom.
R is the H atomic time:
X1 and X2 are compound 1:2 when being identical methyl, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound;
X1 and X2 are that the identical F atomic time is compound 2:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Cl atomic time is compound 3:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Br atomic time is compound 4:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 5:2 the F atomic time, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 6:2 the Cl atomic time, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 7:2 the Br atomic time, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 8:2 the H atomic time, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound;
When R is methyl (CH
3) time:
X1 and X2 are compound 9:2 when being identical methyl, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound;
X1 and X2 are that the identical F atomic time is compound 10:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Cl atomic time is compound 11:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Br atomic time is compound 12:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 13:2 the F atomic time, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 14:2 the Cl atomic time, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 15:2 the Br atomic time, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 16:2 the H atomic time, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound;
When R is methoxymethyl (CH
2OCH
3) time:
X1 and X2 are compound 17:2 when being identical methyl, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound;
X1 and X2 are that the identical F atomic time is compound 18:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Cl atomic time is compound 19:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Br atomic time is compound 20:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 21:2 the F atomic time, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 22:2 the Cl atomic time, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 23:2 the Br atomic time, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 24:2 the H atomic time, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound
Compound of the present invention comprises any three-dimensional chemical isomer with insecticidal activity that meets (A) formula and composition thereof.
The present invention also provides described structure to satisfy the preparation method of the compound of formula (A), and namely described compound can be prepared by following steps:
Structure is satisfied the chrysanthemumic acid acyl chlorides of following formula (Y) and corresponding tetrafluorobenzene carbaldehyde (X) esterification preparation under NaCN exists
Wherein R is H atom, methyl or methoxy methyl (CH
2OCH
3), X1, X2 are that identical methyl, F atom, Cl atom or Br atom or X1 is trifluoromethyl (CF
3), X2 is F atom, Cl atom, Br atom or H atom.
Esterification can be carried out at organic solvents such as toluene, dimethylbenzene, hexanaphthenes, and acyl chlorides (Y) is 0.8:1-1.5:1 with the mol ratio of tetrafluorobenzene carbaldehyde (X), and the mol ratio of NaCN and tetrafluorobenzene carbaldehyde (X) is 1:1.Add simultaneously pyridine as acid binding agent.
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 according to ordinary method, 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 0.01-3.0w/w%.
The liquid form that compound of the present invention is mixed with is missible oil or with hydro carbons, for example kerosene is the solution of solvent.
Described missible oil can add water and admix in disc type insecticidal incense base material when preparation 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 disc type insecticidal 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 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 0.1-0.5w/w%, and 0.1-1w/w% spices is mixed with the solution that contains 0.1-2w/w% 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 new edition 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 the present invention in detail with the form of embodiment, but the present invention is not limited to following examples.Degree in following examples or percentage concentration as not specifying, are weight percent content or weight percent concentration.
Preparation Example 1:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound compound 1 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluorobenzene carbaldehyde 8.9g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane dicarbonyl chloride 11.2g (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 2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound, content 94.8%, yield 91.1% (in aldehyde).The molecular formula of this compound: C
18H
15F
4NO
2, molecular weight: 353.3, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.71 (m, 6H, two key end CH
3C=); 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 4.82 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 6.55 (m, 1H, 4 of phenyl ring-H).
Preparation Example 2:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound compound 2 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluorobenzene carbaldehyde 8.9g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two fluoro-1-vinyl) cyclopropane dicarbonyl chloride 11.67g (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 toluene, obtain compound 2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two fluoro-1-vinyl) cyclopropanecarboxylcompound, content 95.4%, yield 92.5% (in aldehyde).The molecular formula of this compound: C
16H
9F
6NO
2, molecular weight: 361.3, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51
(m, 2H, on the chrysanthemumic acid ring-H); 3.90 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 6.57 (m, 1H, 4 of phenyl ring-H).
Preparation Example 3:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound compound 3 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluorobenzene carbaldehyde 8.9g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two chloro-1-vinyl) cyclopropane dicarbonyl chloride 13.65g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two chloro-1-vinyl) cyclopropanecarboxylcompound, content 95.1%, yield 91.7% (in aldehyde).The molecular formula of this compound: C
16H
9Cl
2F
4NO
2, molecular weight: 394.1, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 5.63 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 6.57 (m, 1H, 4 of phenyl ring-H).
Preparation Example 4:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound compound 4 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluorobenzene carbaldehyde 8.9g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two bromo-1-vinyl) cyclopropane dicarbonyl chloride 18.99g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two bromo-1-vinyl) cyclopropanecarboxylcompound, content 95.3%, yield 90.4% (in aldehyde).The molecular formula of this compound: C
16H
9Br
2F
4NO
2, molecular weight: 483.05, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.32 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 6.57 (m, 1H, 4 of phenyl ring-H).
Preparation Example 5:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound compound 5 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluorobenzene carbaldehyde 8.9g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropane dicarbonyl chloride 14.67g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound, content 96.1%, yield 92.4% (in aldehyde).The molecular formula of this compound: C
17H
9F
8NO
2, molecular weight: 411.24, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 4.91 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 6.57 (m, 1H, 4 of phenyl ring-H).
Preparation Example 6:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound compound 6 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluorobenzene carbaldehyde 8.9g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropane dicarbonyl chloride 15.66g (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 2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound, content 94.6%, yield 91.7% (in aldehyde).The molecular formula of this compound: C
17H
9F
7ClNO
2, molecular weight: 427.7, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.06 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 6.57 (m, 1H, 4 of phenyl ring-H).
Preparation Example 7:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound compound 7 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluorobenzene carbaldehyde 8.9g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropane dicarbonyl chloride 18.33g (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 2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound, content 94.4%, yield 92.7% (in aldehyde).The molecular formula of this compound: C
17H
9F
7BrNO
2, molecular weight: 472.15, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.48 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 6.57 (m, 1H, 4 of phenyl ring-H).
Preparation Example 8:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound compound 8 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluorobenzene carbaldehyde 8.9g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropane dicarbonyl chloride 13.59g (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 2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound, content 95.1%, yield 92.8% (in aldehyde).The molecular formula of this compound: C
17H
10F
7NO
2, molecular weight: 493.15, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 5.93 (m, 1H, two keys-H); 5.70 (m, 1H, two key ends-H); 6.25 (m, 1H, the α position-H); 6.57 (m, 1H, 4 of phenyl ring-H).
Preparation Example 9:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound compound 9 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-tolyl aldehyde 9.6g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane dicarbonyl chloride 11.2g (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 2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound, content 95.3%, yield 92.0% (in aldehyde).The molecular formula of this compound: C
19H
17F
4NO
2, molecular weight: 367.3, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.71 (m, 6H, two key end CH
3C=); 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 4.82 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 2.35 (m, 3H, 4-CH of phenyl ring
3).
Preparation Example 10:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound compound 10 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-tolyl aldehyde 9.6g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two fluoro-1-vinyl) cyclopropane dicarbonyl chloride 11.67g (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 toluene, obtain compound 2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two fluoro-1-vinyl) cyclopropanecarboxylcompound, content 94.9%, yield 91.9% (in aldehyde).The molecular formula of this compound: C
17H
11F
6NO
2, molecular weight: 375.3, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 3.90 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 2.35 (m, 3H, 4-CH of phenyl ring
3).
Preparation Example 11:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound compound 11 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-tolyl aldehyde 9.6g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two chloro-1-vinyl) cyclopropane dicarbonyl chloride 13.65g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two chloro-1-vinyl) cyclopropanecarboxylcompound, content 95.0%, yield 91.9% (in aldehyde).The molecular formula of this compound: C
17H
11Cl
2F
4NO
2, molecular weight: 408.1, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 5.63 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 2.35 (m, 3H, 4-CH of phenyl ring
3).
Preparation Example 12:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound compound 12 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-tolyl aldehyde 9.6g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two bromo-1-vinyl) cyclopropane dicarbonyl chloride 18.99g (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 toluene, obtain compound 2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two bromo-1-vinyl) cyclopropanecarboxylcompound, content 95.2%, yield 91.4% (in aldehyde).The molecular formula of this compound: C
17H
11Br
2F
4NO
2, molecular weight: 497.05, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.32 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 2.35 (m, 3H, 4-CH of phenyl ring
3).
Preparation Example 13:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound compound 13 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-tolyl aldehyde 9.6g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropane dicarbonyl chloride 14.67g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound, content 96.0%, yield 92.7% (in aldehyde).The molecular formula of this compound: C
18H
11F
8NO
2, molecular weight: 425.24, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 4.91 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 2.35 (m, 3H, 4-CH of phenyl ring
3).
Preparation Example 14:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound compound 14 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-tolyl aldehyde 9.6g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropane dicarbonyl chloride 15.66g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound, content 95.2%, yield 91.1% (in aldehyde).The molecular formula of this compound: C
18H
11F
7ClNO
2, molecular weight: 441.7, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.06 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 2.35 (m, 3H, 4-CH of phenyl ring
3).
Preparation Example 15:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound compound 15 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-tolyl aldehyde 9.6g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropane dicarbonyl chloride 18.33g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound, content 95.2%, yield 93.7% (in aldehyde).The molecular formula of this compound: C
18H
11F
7BrNO
2, molecular weight: 486.15, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.48 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 2.35 (m, 3H, 4-CH of phenyl ring
3).
Preparation Example 16:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl 1-vinyl) cyclopropanecarboxylcompound compound 16 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-tolyl aldehyde 9.6g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropane dicarbonyl chloride 13.59g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound, content 94.3%, yield 93.5% (in aldehyde).The molecular formula of this compound: C
18H
12F
7NO
2, molecular weight: 407.15, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 5.93 (m, 1H, two keys-H); 5.70 (m, 1H, two key ends-H); 6.25 (m, 1H, the α position-H); 2.35 (m, 3H, 4 of phenyl ring-CH3).
Preparation Example 17:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound compound 17 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-methoxy methyl benzaldehyde 11.1g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropane dicarbonyl chloride 11.2g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound, content 95.6%, yield 93.1% (in aldehyde).The molecular formula of this compound: C
20H
19F
4NO
3, molecular weight: 397.3, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.71 (m, 6H, two key end CH
3C=); 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 4.82 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 4.63 (m, 2H, 4-CH of phenyl ring
2O-); 3.24 (m, 3H, 4-OCH of phenyl ring
3).
Preparation Example 18:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound compound 18 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-methoxy methyl benzaldehyde 11.1g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two fluoro-1-vinyl) cyclopropane dicarbonyl chloride 11.67g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two fluoro-1-vinyl) cyclopropanecarboxylcompound, content 93.8%, yield 92.7% (in aldehyde).The molecular formula of this compound: C
18H
13F
6NO
3, molecular weight: 405.3, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 3.90 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 4.63 (m, 2H, 4-CH of phenyl ring
2O-); 3.24 (m, 3H, 4-OCH of phenyl ring
3).
Preparation Example 19:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound compound 19 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-methoxy methyl benzaldehyde 11.1g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two chloro-1-vinyl) cyclopropane dicarbonyl chloride 13.65g (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 toluene, obtain compound 2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two chloro-1-vinyl) cyclopropanecarboxylcompound, content 95.0%, yield 91.9% (in aldehyde).The molecular formula of this compound: C
18H
13Cl
2F
4NO
3, molecular weight: 438.1, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 5.63 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 4.63 (m, 2H, 4-CH of phenyl ring
2O-); 3.24 (m, 3H, 4-OCH of phenyl ring
3).
Preparation Example 20:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound compound 20 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-methoxy methyl benzaldehyde 11.1g (0.05mol), pyridine 5g is 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 2,2-dimethyl-3-(2 in lower 2 hours, 2-two bromo-1-vinyl) cyclopropane dicarbonyl chloride 18.99g (0.06mol) drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-two bromo-1-vinyl) cyclopropanecarboxylcompound, content 94.9%, yield 91.8% (in aldehyde).The molecular formula of this compound: C
18H
13Br
2F
4NO
3, molecular weight: 527.05, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.32 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 4.63 (m, 2H, 4-CH of phenyl ring
2O-); 3.24 (m, 3H, 4-OCH of phenyl ring
3).
Preparation Example 21:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound compound 21 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-methoxy methyl benzaldehyde 11.1g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropane dicarbonyl chloride 14.67g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound, content 94.5%, yield 91.6% (in aldehyde).The molecular formula of this compound: C
19H
13F
8NO
3, molecular weight: 455.24, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 4.91 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 4.63 (m, 2H, 4-CH of phenyl ring
2O-); 3.24 (m, 3H, 4-OCH of phenyl ring
3).
Preparation Example 22:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound compound 22 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-methoxy methyl benzaldehyde 11.1g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropane dicarbonyl chloride 15.66g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound, content 94.0%, yield 92.1% (in aldehyde).The molecular formula of this compound: C
19H
13F
7ClNO
3, molecular weight: 471.7, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.06 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 4.63 (m, 2H, 4-CH of phenyl ring
2O-); 3.24 (m, 3H, 4-OCH of phenyl ring
3).
Preparation Example 23:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound compound 23 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-methoxy methyl benzaldehyde 11.1g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropane dicarbonyl chloride 18.33g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound, content 94.9%, yield 92.7% (in aldehyde).The molecular formula of this compound: C
19H
13F
7BrNO
3, molecular weight: 516.15, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 6.48 (m, 1H, two keys-H); 6.25 (m, 1H, the α position-H); 4.63 (m, 2H, 4-CH of phenyl ring
2O-); 3.24 (m, 3H, 4-OCH of phenyl ring
3).
Preparation Example 24:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound compound 24 synthetic
In the four-hole bottle of a 200ml, drop into 2,3,5,6-tetrafluoro-4-methoxy methyl benzaldehyde 11.1g (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, throw to finish and stir 10min, 10-20 ℃ slowly drips 2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropane dicarbonyl chloride 13.59g (0.06mol) in lower 2 hours, drips 30 ℃ of reactions of Bi Shengzhi 4 hours.Organic phase successively with each washing of 50ml5% 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 2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound, content 94.3%, yield 93.2% (in aldehyde).The molecular formula of this compound: C
19H
14F
7NO
3, molecular weight: 437.15, nuclear magnetic resonance spectrum (
1H (ppm) CDCl
3) 1.11 (m, 6H, ring-CH
3); 1.06-1.51 (m, 2H, on the chrysanthemumic acid ring-H); 5.93 (m, 1H, two keys-H); 5.70 (m, 1H, two key ends-H); 6.25 (m, 1H, the α position-H); 4.63 (m, 2H, 4-CH of phenyl ring
2O-); 3.24 (m, 3H, 4-OCH of phenyl ring
3).
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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 1 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense I that had 0.08w/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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 3 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense II that had 0.08w/w% compound 3 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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 4 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense III that had 0.08w/w% compound 4 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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 6 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense IV that had 0.08w/w% compound 6 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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 9 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense V that had 0.08w/w% compound 9 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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 11 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense VI that had 0.08w/w% compound 11 in 3 hours to obtain a cover.
Application Example 7
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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 12 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense VII that had 0.08w/w% compound 12 in 3 hours to obtain a cover.
Application Example 8
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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 17 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense VIII that had 0.08w/w% compound 17 in 3 hours to obtain a cover.
Application Example 9
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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 19 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense IX that had 0.08w/w% compound 19 in 3 hours to obtain a cover.
Application Example 10
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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 20 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense X that had 0.08w/w% compound 20 in 3 hours to obtain a cover.
Application Example 11
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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 22 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense XI that had 0.08w/w% compound 22 in 3 hours to obtain a cover.
Application Example 12
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 99.92 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 0.4w/v% solution of preparation compound 24 in kerosene.
Evenly drip the 8ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense XII that had 0.08w/w% compound 24 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 99.2 weight parts to be shaped, then oven dry forms line spices shape insecticidal incense base materials (diameter 12.0cm, thick 4mm, a counterweight 40g).
On the other hand, the 4.0w/v% solution of preparation Es-esbiothrin in kerosene.
Evenly drip the 4ml mentioned solution with micro-syringe on this cover line spices base material, then at room temperature place the disc type insecticidal incense that had the 0.4w/w%Es-esbiothrin in 3 hours to obtain a cover.
Test implementation example 1
With the disc type insecticidal incense of Application Example 1-12 and reference example 1 according to GB13917.4-92
-Carry out kill mosquito evaluation of pesticide effectiveness contrast, 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 24hr.
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) | 24h mortality ratio (%) |
| Insecticidal incense I | Compound 1 | 0.08 | 7.68 | 100 |
| Insecticidal incense II | Compound 3 | 0.08 | 11.86 | 100 |
| Insecticidal incense III | Compound 4 | 0.08 | 10.16 | 95 |
| Insecticidal incense IV | Compound 6 | 0.08 | 9.33 | 100 |
| Insecticidal incense V | Compound 9 | 0.08 | 12.25 | 100 |
| Insecticidal incense VI | Compound 11 | 0.08 | 8.20 | 100 |
| Insecticidal incense VII | Compound 12 | 0.08 | 10.68 | 100 |
| Insecticidal incense VIII | Compound 17 | 0.08 | 10.27 | 95 |
| Insecticidal incense IX | Compound 19 | 0.08 | 4.02 | 100 |
| Insecticidal incense X | Compound 20 | 0.08 | 4.75 | 100 |
| Insecticidal incense XI | Compound 22 | 0.08 | 5.13 | 100 |
| Insecticidal incense XII | Compound 24 | 0.08 | 6.55 | 100 |
| The reference insecticidal incense | The Es-esbiothrin | 0.4 | 6.35 | 100 |
Result shows, compound 19 and 20 relative effectivenes be at more than 8 times of Es-esbiothrin, and compound 22 and 24 relative effectivenes be at more than 5 times of Es-esbiothrin, and other compound also has and kills preferably the mosquito activity.
Application Example 13
With containing 2mg compound 19,15mg 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 14
With containing 2mg compound 20,15mg 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 15
With containing 2mg compound 22,15mg 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 16
With containing 2mg compound 24,15mg 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 10mg prallethrin, 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.
Test implementation example 2
The prallethrin electric mosquito repellent tablet of 10mg/ sheet at present the most frequently used in Application Example 13-16 of the present invention and reference example 2 is carried 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 prallethrin electric mat effect
Result shows: the relative effectivenes of the electric mat for preparing for former medicine take the compounds of this invention 19,20,22,24 is in 5 times of left and right of prallethrin chrysanthemum ester anti-mosquito incense sheet.
Application Example 17
With 0.2 weight part compound 19 and 3 parts of BHT of 0. weight part, the spices of 0.3 weight part, the n-tetradecane of 99.2 weight parts are combined and are prepared into mosquito liquid under heating.Then can becomes electric liquid device, wherein contains compound 19 0.2w/w%.
Application Example 18
With 0.2 weight part compound 20 and 0.3 weight part BHT, the spices of 0.3 weight part, the n-tetradecane of 99.2 weight parts are combined and are prepared into mosquito liquid under heating.Then can becomes electric liquid device, wherein contains compound 20 0.2w/w%.
Application Example 19
With 0.2 weight part compound 22 and 0.3 weight part BHT, the spices of 0.3 weight part, the n-tetradecane of 99.2 weight parts are combined and are prepared into mosquito liquid under heating.Then can becomes electric liquid device, wherein contains compound 22 0.2w/w%.
Application Example 20
With 0.2 weight part compound 24 and 0.3 weight part BHT, the spices of 0.3 weight part, the n-tetradecane of 99.2 weight parts are combined and are prepared into mosquito liquid under heating.Then can becomes electric liquid device, wherein contains compound 24 0.2w/w%.
Reference example 3
With 1.0 weight part prallethrins and 0.3 weight part BHT, the spices of 0.3 weight part, the n-tetradecane of 98.4 weight parts are combined and are prepared into mosquito liquid under heating.Then can becomes electric liquid device, wherein contains prallethrin 1.0w/w%.
Test implementation example 3
With in Application Example 17-20 of the present invention and reference example 3 at present the most frequently used 1% prallethrin electric liquid device carry 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 of table 3. the compounds of this invention preparation and the comparison of prallethrin vaporizer mosquito liquid effect
Result shows: the compounds of this invention 19,20,22,24 be that the relative effectivenes of the vaporizer mosquito liquid for preparing of former medicine is at more than 5 times of prallethrin chrysanthemum ester vaporizer mosquito liquid.
Application Example 21
Kerosene with 0.3 weight part compound 19 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 190.3w/w%.
Application Example 22
Kerosene with 0.3 weight part compound 20 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 20 0.3w/w%.
Application Example 23
Kerosene with 0.3 weight part compound 24 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 24 0.3w/w%.
Test implementation example 4
Application Example 21,22,23 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 4-6:
The insect aerosol of table 4. compound 19 preparation is to mosquito, fly, the insect killing effect of Groton bug
| Insect | KT50 (mosquito/fly/cockroach) | 24 hours mortality ratio |
| Mosquito | 6.05 minute | 100％ |
| Fly | 8.02 minute | 100％ |
| Groton bug | 5.24 minute | 100％(72h) |
The insect aerosol of table 5. compound 20 preparation is to mosquito, fly, the insect killing effect of Groton bug
| Insect | KT50 (mosquito/fly/cockroach) | 24 hours mortality ratio |
| Mosquito | 4.90 minute | 100％ |
| Fly | 7.32 minute | 100％ |
| Groton bug | 5.36 minute | 100％(72h) |
The insect aerosol of table 6. compound 24 preparation is to mosquito, fly, the insect killing effect of Groton bug
| Insect | KT50 (mosquito/fly/cockroach) | 24 hours mortality ratio |
| Mosquito | 5.75 minute | 100％ |
| Fly | 7.45 minute | 100％ |
| Groton bug | 6.04 minute | 100％(72h) |
Result shows: the aerosol of the compounds of this invention 19,20,24 preparations is to mosquito, and fly, Groton bug have good insect killing effect.
Claims (9)
1. structural formula is the pyrethroid compound of formula (A), and (A) is as follows for formula:
Wherein R is H atom, methyl or methoxy methyl (CH
2OCH
3), X1, X2 are identical methyl, F atom, Cl atom or Br atom, perhaps X1 is trifluoromethyl (CF
3), X2 is F atom, Cl atom, Br atom or H atom.
2. pyrethroid compound according to claim 1 is characterized in that: when R is the H atomic time:
X1 and X2 are compound 1:2 when being identical methyl, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound;
X1 and X2 are that the identical F atomic time is compound 2:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Cl atomic time is compound 3:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Br atomic time is compound 4:2,3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 5:2 the F atomic time, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 6:2 the Cl atomic time, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 7:2 the Br atomic time, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 8:2 the H atomic time, 3,5,6-tetrafluoro-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound;
When R is methyl (CH
3) time:
X1 and X2 are compound 9:2 when being identical methyl, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound;
X1 and X2 are that the identical F atomic time is compound 10:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Cl atomic time is compound 11:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Br atomic time is compound 12:2,3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 13:2 the F atomic time, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 14:2 the Cl atomic time, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 15:2 the Br atomic time, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 16:2 the H atomic time, 3,5,6-tetrafluoro-4-methyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound;
When R is methoxymethyl (CH
20CH
3) time:
X1 and X2 are compound 17:2 when being identical methyl, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-methyl-1-propylene base) cyclopropanecarboxylcompound;
X1 and X2 are that the identical F atomic time is compound 18:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Cl atomic time is compound 19:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 and X2 are that the identical Br atomic time is compound 20:2,3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2,2-, two bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 21:2 the F atomic time, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-fluoro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 22:2 the Cl atomic time, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-chloro-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 23:2 the Br atomic time, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-trifluoromethyl-2-bromo-1-vinyl) cyclopropanecarboxylcompound;
X1 is-CF
3, X2 is to be compound 24:2 the H atomic time, 3,5,6-tetrafluoro-4-methoxymethyl-alpha-cyano benzyl-2,2-dimethyl-3-(2-Trifluoromethyl-1-vinyl) cyclopropanecarboxylcompound.
3. pyrethroid compound according to claim 1 and 2, is characterized in that comprising any single three-dimensional chemical isomer or its mixture that represent with (A) formula.
4. the application of the described pyrethroid compound of claim 1 or 2 aspect the control sanitary insect pest; Described sanitary insect pest is mosquito, fly or Groton bug.
5. the application of pyrethroid compound according to claim 4 is characterized in that: the compound that satisfies (A) with described structure is prepared into various forms of sterilants as former medicine according to ordinary method, is used for except killing mosquito, fly or Groton bug.
6. the application of pyrethroid compound according to claim 5 is characterized in that: described various forms of sterilants comprise disc type insecticidal incense, electric mosquito repellent tablet, electric liquid device or insect aerosol.
7. the application of pyrethroid compound according to claim 6 is characterized in that: described disc type insecticidal incense is mixed with compound (A) to join in base material after liquid form and makes, and wherein the content of compound (A) is 0.01-3.0w/w%; The liquid form that described compound (A) is mixed with is missible oil or the solution take hydro carbons as solvent; Described base material 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.
8. the application of pyrethroid compound according to claim 6, it is characterized in that: described electric mosquito repellent tablet is will contain the solution dropping of compound (A) and/or be coated on the porosity base material to make, and the content of compound in described anti-mosquito incense sheet (A) is the 1-20mg/ sheet; Described porous substrate 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; Also contain the additive that is selected from antioxidant, stifling conditioning agent, spices or dyestuff in the described solution that contains compound (A).
9. the application of pyrethroid compound according to claim 6, it is characterized in that: described electric liquid device is that compound (A) is dissolved in aliphatic hydrocarbon, then the antioxidant that adds 0.1-0.5w/w%, 0.1-1w/w% spices is mixed with the solution that contains 0.1-2w/w% compound (A) and obtains; Described aliphatic hydrocarbon is the aliphatic hydrocarbon of C14 component.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258202A (en) * | 1978-02-28 | 1981-03-24 | Montedison S.P.A. | Cyclopropanecarboxylic acids and esters |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| JP2002249464A (en) * | 2001-02-22 | 2002-09-06 | Sumitomo Chem Co Ltd | Ester compound and harmful organism preventive agent containing the same as active ingredient |
-
2008
- 2008-11-19 CN CN 200810181007 patent/CN101735104B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4258202A (en) * | 1978-02-28 | 1981-03-24 | Montedison S.P.A. | Cyclopropanecarboxylic acids and esters |
| US4332815A (en) * | 1979-06-25 | 1982-06-01 | Fmc Corporation | Insecticidal perhaloalkylvinylcyclopropanecarboxylates |
| JP2002249464A (en) * | 2001-02-22 | 2002-09-06 | Sumitomo Chem Co Ltd | Ester compound and harmful organism preventive agent containing the same as active ingredient |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2002249464A 2002.09.06 |
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