CN102134195A - Ester compound for desinsection - Google Patents

Ester compound for desinsection Download PDF

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Publication number
CN102134195A
CN102134195A CN2010100026785A CN201010002678A CN102134195A CN 102134195 A CN102134195 A CN 102134195A CN 2010100026785 A CN2010100026785 A CN 2010100026785A CN 201010002678 A CN201010002678 A CN 201010002678A CN 102134195 A CN102134195 A CN 102134195A
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formula
alkyl
propenyl
fluoro
tetrafluoro
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Inventor
戚明珠
贺书泽
徐海鹏
朱建荣
周景梅
姜友法
吕杨
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Jiangsu Yangnong Chemical Co Ltd
Youth Chemical Co Ltd
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Jiangsu Yangnong Chemical Co Ltd
Youth Chemical Co Ltd
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Priority to CN201510131118.2A priority Critical patent/CN104788315B/en
Priority to CN2010100026785A priority patent/CN102134195A/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/32—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring
    • C07C255/38—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups
    • C07C255/39—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms having cyano groups bound to acyclic carbon atoms of a carbon skeleton containing at least one six-membered aromatic ring the carbon skeleton being further substituted by esterified hydroxy groups with hydroxy groups esterified by derivatives of 2,2-dimethylcyclopropane carboxylic acids, e.g. of chrysanthemumic acids

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention provides an ester compound with insecticidal activity. The structural formula of the ester compound is shown in a formula (I) or (II), wherein Z1 is hydrogen atom, cyan, acetenyl or nitro; R1 is hydrogen atom, cyan, halogen atom, hydroxyl, nitro, amido, C1-C4 alkyl or halogenated alkyl, or group -(CH2)m-X-R1', wherein m is equal to 0 or 1, X is oxygen atom or sulfur atom, and R1' is C1-C4 alkyl or halogenated alkyl; X1 is cyan, monofluoromethyl, difluoromethyl, C2-C4 unsaturated alkyl or halogenated alkyl; Z2 is hydrogen atom, cyan, acetenyl or nitro; n is an integral of 1-4; and R2 is cyan, halogen atom, hydroxyl, nitro, amido, halogenated methyl, C2-C4 alkyl or halogenated alkyl, or group -(CH2)q-X2-R2', wherein q is equal to 0 or 2, X2 is oxygen atom or sulfur atom, R2' is halogenated alkyl, C2-C4 alkyl or halogenated alkyl. The compound has excellent activity of killing pests, can be used as an effective component of a pest control agent. The invention also provides a preparation method of the compound and application of the compound in the aspect of controlling the pests.

Description

Can be used for parasiticidal ester cpds
Technical field
The present invention relates to a kind of parasiticidal ester cpds that can be used for, and preparation method thereof and the application in pest control.
Background technology
Pyrethroid coumpound can be used for pest control, and this is widely known by the people.Because it has efficiently, low toxicity, low residue, environment compatibility are good, obtained application widely in the prevention and control field of sanitary insect pest.But growth along with duration of service, mosquitos and flies has produced certain resistance (Gao Xiwu etc. to some traditional pyrethroid products (as esbiothrin) etc., Chinese media biology and control magazine, 2004,15 (2), 105), the former dose of pyrethroid that needs to add in products such as mosquito-repellent incense or aerosol for prevention effect same before reaching has increased greatly.This has not only improved production cost, has also increased the weight of environmental pressure.
We by the structure of modification to traditional pyrethroid acid, alcohol moiety, have formed the fluorine-containing pyrethroid compound of a series of novelties in CN101381306A, CN101492393A.These compounds have certain drug effect to insect, and it is lower to have overcome traditional pyrethroid activity, and pest control produces the shortcoming of high resistance.We have prepared the pyrethroid compound of a series of novel structures on this basis, have filtered out highly active kind, have further expanded the scope of pest control, have better application to be worth in sterilant.
In addition, often have asymmetric C atom in the pyrethroid compound structure, can produce various steric isomers thus, wherein the steric isomer of certain ad hoc structure tends to the activity higher than racemoid.From the angle of environmental protection, use highly active isomer can under the prerequisite that does not reduce drug effect, reduce the dose of using, thereby reduce toxicity non-target organism, improve security, reduce the left drug environmental pollution.Based on such thinking, we also study the activity of each steric isomer in the compound among the present invention, find in this compounds, when on the alcohol moiety α position substituted radical being arranged, α position C atom be configured as the S type time activity often higher; Two substituting groups are positioned at trans position on the acid moieties cyclopropane, and the isomeric compound that 1 carbonoid is the R configuration is often active higher; Isomeric compound when the two key steric configurations of acid moieties are the Z configuration is often active higher.
Summary of the invention
Purpose of the present invention just provides a kind of parasiticidal ester cpds that can be used for, to improve the effect of insecticide control insect.
The present invention also provides the preparation method of described ester cpds and as the application of pesticide active ingredient.
The technical scheme that the present invention proposes is as follows:
A kind of ester cpds with insecticidal activity is provided, and its structure is as shown in the formula shown in (I) or the formula (II):
Figure G2010100026785D00021
Wherein,
Z1 is hydrogen atom, cyano group, ethynyl or nitro;
R1 is hydrogen atom, cyano group, halogen atom, hydroxyl, nitro, amido, C1-C4 alkyl or halo alkyl or group-(CH 2) m-X-R1 ': m=0 or 1 wherein, X is Sauerstoffatom or sulphur atom, R1 ' is C1-C4 alkyl or halo alkyl;
X1 is unsaturated alkyl or the halo alkyl of cyano group, a methyl fluoride, difluoromethyl or C2-C4;
Wherein,
Z2 is hydrogen atom, cyano group, ethynyl or nitro;
N is the integer of 1-4;
R2 is cyano group, halogen atom, hydroxyl, nitro, amido, halogenated methyl, C2-C4 alkyl or halo alkyl or group-(CH 2) q-X2-R2 ': q=0 or 1 wherein, X2 is Sauerstoffatom or sulphur atom, R2 ' is halogenated methyl, C2-C4 alkyl or halo alkyl;
Compound shown in described formula (I) or the formula (II) can be their any one three-dimensional chemical isomer, also can be the mixture of these steric isomers.
In the compound shown in described formula (I) or the formula (II), preferred compound title and structure are as follows:
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(3,3-two fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure G2010100026785D00023
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(3-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure G2010100026785D00031
2,3,5,6-tetrafluoro-4-propenyl-alpha-cyano benzyl-3-(2-cyano group-1-vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
2,3,4,5,6-PFBBR-3-(2-ethynyl-1-vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
2,3,5,6-tetrafluoro-4-propenyl benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure G2010100026785D00034
2,3,5,6-tetrafluoro-4-proyl benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure G2010100026785D00041
2,3,4,5,6-PFBBR-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure G2010100026785D00042
2,3,5,6-tetrafluoro-4-acetylene oxy-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure G2010100026785D00043
Perhaps
2,3,5,6-tetrafluoro-4-acetylene oxygen methyl-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure G2010100026785D00044
Further, can be preferably following these highly active steric isomers:
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-Z-(1R, trans)-3-(3,3-two fluoro-1-propenyl)-2,2-dimethylcyclopropane carboxylic;
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-Z-(1R, trans)-3-(3-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
2,3,5,6-tetrafluoro-4-proyl benzyl-Z-(1R, trans)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
2,3,5,6-tetrafluoro-4-acetylene oxy-benzyl-Z-(1R, trans)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester; Perhaps
2,3,5,6-tetrafluoro-4-acetylene oxygen methyl-benzyl-Z-(1R, trans)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
The present invention also provides the preparation method of described ester cpds.
In the described ester cpds, the ester cpds synthetic method shown in the formula (I) is as follows:
By the acid shown in the pure and mild formula (B) shown in the formula (A) according to 0.8～1.2: 1 mol ratio, in organic solvent, under 60-130 ℃, sulfuric acid or Catalyzed by p-Toluenesulfonic Acid, carry out esterification and obtain; Wherein, the mol ratio of the alcohol shown in catalyst sulfuric acid or tosic acid and the formula (A) is 0.01～0.1: 1; Perhaps
, made with the pure esterification reaction shown in the formula (A) after the chloride reagent chloride obtains the acyl chlorides shown in the formula (C) by the acid shown in the formula (B), wherein the mol ratio of the acyl chlorides shown in the pure and mild formula (C) shown in (A) is 0.8～1.2: 1 again.
Wherein,
Z1 is hydrogen atom, cyano group, ethynyl or nitro;
R1 is hydrogen atom, cyano group, halogen atom, hydroxyl, nitro, amido, C1-C4 alkyl or halo alkyl or group-(CH 2) m-X-R1 ': m=0 or 1 wherein, X is Sauerstoffatom or sulphur atom, R1 ' is C1-C4 alkyl or halo alkyl;
Wherein,
X1 is unsaturated alkyl or the halo alkyl of cyano group, a methyl fluoride, difluoromethyl, C2-C4;
Figure G2010100026785D00062
Wherein,
X1 is unsaturated alkyl and the halo alkyl of cyano group, a methyl fluoride, difluoromethyl, C2-C4.
In the described ester cpds, the ester cpds synthetic method shown in the formula (II) is as follows:
By the acid shown in the pure and mild formula (E) shown in the formula (D) according to 0.8～1.2: 1 mol ratio, in organic solvent, under 60-130 ℃, sulfuric acid or Catalyzed by p-Toluenesulfonic Acid, carry out esterification and obtain; Wherein, the mol ratio of the alcohol shown in catalyst sulfuric acid or tosic acid and the formula (D) is 0.01～0.1: 1; Perhaps
, made with the pure esterification reaction shown in the formula (D) after the chloride reagent chloride obtains the acyl chlorides shown in the formula (F) by the acid shown in the formula (E), wherein the mol ratio of the acyl chlorides shown in the pure and mild formula (F) shown in (D) is 0.8～1.2: 1 again;
Figure G2010100026785D00063
Wherein,
Z2 is hydrogen atom, cyano group, ethynyl or nitro;
N is the integer of 1-4;
R2 is cyano group, halogen atom, hydroxyl, nitro, amido, halogenated methyl, C2-C4 alkyl or halo alkyl or group-(CH 2) q-X2-R2 ': q=0 or 1 wherein, X2 is Sauerstoffatom or sulphur atom, R2 ' is halogenated methyl, C2-C4 alkyl or halo alkyl;
Figure G2010100026785D00071
More than (A) and (D) alcohol of formula, in documents such as Chinese patent CN1044936A and CN1044650A, all mention, be known compound, can or directly buy commercially available reagent with reference to the preparation of the preparation method in the above-mentioned document; (E) compound of formula is a known compound, can prepare or directly buy commercially available reagent with reference to the method for prior art; (B) acid of formula can be synthetic with reference to several different methods of the prior art, for example with reference to the method among the CN101100445, with aldehydo-ester shown in (G) formula and wittig reagent (C 6H 5) 3P+-CH 2X1-in anhydrous organic solvents such as tetrahydrofuran (THF) with 0.8～1.2: 1 mol ratio is 0～40 ℃ of down reaction 5～20 hours, and the compound that obtains formula (H) hydrolysis again obtains;
Figure G2010100026785D00072
Wherein, X1 is unsaturated alkyl or the halo alkyl of cyano group, a methyl fluoride, difluoromethyl, C2-C4.
The compound of the formula of the present invention (I) by the preparation of above method is listed in the table 1.
Figure G2010100026785D00073
The compound of the formula of the present invention (II) by the preparation of above method is listed in the table 2
Figure G2010100026785D00074
Figure G2010100026785D00091
Figure G2010100026785D00101
Figure G2010100026785D00111
Figure G2010100026785D00121
Figure G2010100026785D00141
The present invention also provides the application of described ester cpds.
Ester cpds of the present invention can be used as the pesticide active ingredient of pest control and uses.
Described insect comprises insects such as the insect, nematode, acarid of public health insect such as mosquito, fly, cockroach and harm agriculture production.For example Dulicidae culex pipiens pollens, Culex tritaeniorhynchus, Culex quinquefasciatus, Culex molestus etc.; Aedes such as Aedes aegypti, informal voucher yellow-fever mosquito etc.; Armigeres such as armigeres obturbans; Anopheles such as Anopheles sinensis, anopheles minius, just than inferior anopheles etc.; Sting fly; Heleidae; Chironomidae; Nuscidae such as housefly, false stable fly etc.; Calliphoridae; The sarcophagid Superfamily; Fly etc. is planted on Anthomyiidae such as delia platura, Fannia canicularis, green onion ground; Tephritidae; Drosophilidae; Simulidae; Tabanidae.
In the application as the pesticide active ingredient of pest control, described ester cpds can with other sterilants such as esbiothrin, propine chrysanthemum ester, Tetramethrin, lambda-cyhalothrin, Chlorpyrifos 94, Avrmectin, thiophene worm piperazine, Rynaxypyr, Flubendiamide as the composite use of insecticidal active ingredient.Can be prepared into mosquito-repellent incense, electric liquid device, electric mat, aerosol or be fit to multiple hygienic biocide goods such as resin lacing film that volatilization at normal temperatures uses, filter paper ribbon, fan mosquito-repellent incense; Also can add and be prepared into all kinds of agricultural chemicals such as pulvis, granule, emulsion after agricultural goes up acceptable inert support, tensio-active agent and solvent.
Embodiment
Explain technical scheme of the present invention and effect in detail with the form of embodiment below, but the present invention is not limited to following examples.
Preparation embodiment 1:
3-(3,3-two fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid's preparation (compound 84,85,87,88 acid moieties)
In the four-hole bottle of a 250ml, drop into 3-aldehyde radical-2,2-dimethyl cyclopropane carboxylic acid methyl esters 15.6g (0.1mol), the 50ml anhydrous tetrahydro furan adds the 0.5g potassium tert.-butoxide again, drips 32.7g (0.1mol) (C while stirring under 5 ℃ 6H 5) 3P+-CH 2CHF 2-be dissolved in the suspension liquid of 80ml tetrahydrofuran (THF), drip in 2 hours and finish, be warming up to 20 ℃ of reactions 8 hours then.Slough tetrahydrofuran (THF) under the 50mmHg negative pressure, add 100ml toluene, respectively with 200ml washing twice, tell toluene layer and add the sodium hydroxide solution of 100g 10%, stir and be heated to 80 ℃ of reactions 2 hours down, be cooled to room temperature, branch removes toluene layer.Water layer is transferred in the 250ml there-necked flask, the ice-water bath insulation drips 30% sulphuric acid soln 100g down, keeps temperature to be lower than 5 ℃, and dripping to finish has a large amount of canescence flockss to separate out, filter, get 20ml clear water washing solid twice, obtain being heated to 100 ℃ under the negative pressure after air-dry to purify solvent toluene, obtain 3-(3,3-two fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acid 14.9g, content is 94.8%, yield 72.6%.
Preparation embodiment 2:
2,3,5,6-tetrafluoro-4-propenyl-S-alpha-cyano benzyl-3-(2-cyano group-1-vinyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 1)
In the flask of a 500ml, drop into 3-(2-cyano group-1-vinyl)-2,2-dimethyl cyclopropane carboxylic acid 16.5g (0.1mol), 2,3,5,6-tetrafluoro-4-propenyl-S-Cyanobenzyl Alcohol 26.6g (0.11mol), 180ml toluene, load onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, with the 100g washing once, dilute hydrochloric acid with 100g 5% washs once again, uses the sodium hydrogen carbonate solution of 100g 5% to wash once, and last 100g water washs once again, collecting toluene layer is heated to 100 ℃ and purifies solvent toluene and obtain compound 1 weight 37.3g, content 97.3% under the 10mmHg negative pressure.The molecular formula of this compound: C 20H 16F 4O 2N 2Molecular weight 392, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 3.22 (d, 2H); 4.93 (m, 2H); 5.31 (s, 1H); 6.07 (m, 1H); 6.25 (s, 1H); 6.30 (m, 1H) specific rotation α=+ 21.4 degree.
Preparation embodiment 3:
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(3-fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 75)
In the flask of a 500ml, drop into 3-(3-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 17.2g (0.1mol), 2,3,5,6-tetrafluoro-4-methoxyl methyl benzylalcohol 22.4g (0.1mol), 180ml toluene, load onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, with the 100g washing once, dilute hydrochloric acid with 100g 5% washs once again, uses the sodium hydrogen carbonate solution of 100g 5% to wash once, and last 100g water washs once again, collecting toluene layer is heated to 100 ℃ and purifies solvent toluene and obtain compound 75 weight 33.2g, content 96.5% under the 10mmHg negative pressure.The molecular formula of this compound: C 18H 19F 5O 3Molecular weight 378, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 3.24 (s, 3H); 4.63 (s, 2H); 4.76 (t, 1H); 5.31 (m, 1H); 5.34 (s, 2H); 5.68 (m, 2H).
Preparation embodiment 4:
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R, trans-Z-3-(3-fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 76)
In the flask of a 500ml, drop into 1R, trans-Z-3-(3-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 17.2g (0.1mol), 2,3,5,6-tetrafluoro-4-methoxyl methyl benzylalcohol 22.4g (0.1mol), 180ml toluene, load onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, and with the 100g washing once, the dilute hydrochloric acid with 100g 5% washs once again, sodium hydrogen carbonate solution with 100g 5% washs once, last 100g water washs once again, collects toluene layer and is heated to 100 ℃ purifies solvent toluene and obtain compound 76 weight 31.6g, content 98.2% under the 10mmHg negative pressure.The molecular formula of this compound: C 18H 19F 5O 3Molecular weight 378, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 3.24 (s, 3H); 4.63 (s, 2H); 4.88 (t, 1H); 5.31 (m, 1H); 5.34 (s, 2H); 5.68 (m, 2H), specific rotation α=+ 18.7 degree.
Preparation embodiment 5:
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-1R, trans-Z-3-(3,3-two fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 86)
In the flask of a 500ml, drop into 1R, trans-Z-3-(3-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 19.0g (0.1mol), 2,3,5,6-tetrafluoro-4-methoxyl methyl benzylalcohol 22.4g (0.1mol), 180ml toluene, load onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, and with the 100g washing once, the dilute hydrochloric acid with 100g 5% washs once again, sodium hydrogen carbonate solution with 100g 5% washs once, last 100g water washs once again, collects toluene layer and is heated to 100 ℃ purifies solvent toluene and obtain compound 86 weight 34.2g, content 97.4% under the 10mmHg negative pressure.The molecular formula of this compound: C 18H 18F 6O 3Molecular weight 396, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 3.24 (s, 3H); 4.63 (s, 2H); 4.76 (t, 1H); 5.34 (s, 2H); 5.64 (m, 1H); 5.64 (m, 1H); 5.70 (m, 1H); 5.84 (m, 1H), specific rotation α=+ 19.2 degree.
Preparation embodiment 6:
2,3,4,5,6-PFBBR-3-(3,3,3-three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 109)
In the flask of a 500ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol), 2,3,4,5,6-five fluoro benzyl alcohol 19.8g (0.1mol), 180ml toluene, load onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, and with the 100g washing once, the dilute hydrochloric acid with 100g 5% washs once again, sodium hydrogen carbonate solution with 100g 5% washs once, last 100g water washs once again, collects toluene layer and is heated to 100 ℃ purifies solvent toluene and obtain compound 109 weight 33.1g, content 98.1% under the 10mmHg negative pressure.The molecular formula of this compound: C 16H 12F 8O 2Molecular weight 388, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 5.34 (s, 2H); 5.70 (m, 1H); 5.93 (m, 1H).
Preparation embodiment 7:
2,3,5,6-tetrafluoro-4-proyl benzyl-3-(3,3,3-three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 120)
In the flask of a 500ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 20.8g (0.1mol), 2,3,5,6-tetrafluoro-4-proyl benzylalcohol 21.8g (0.1mol), 180ml toluene is loaded onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, with the 100g washing once, dilute hydrochloric acid with 100g 5% washs once again, uses the sodium hydrogen carbonate solution of 100g 5% to wash once, and last 100g water washs once again, collecting toluene layer is heated to 100 ℃ and purifies solvent toluene and obtain compound 120 weight 37.1g, content 97.1% under the 10mmHg negative pressure.The molecular formula of this compound: C 19H 15F 7O 2Molecular weight 408, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 1.82 (t, 1H); 3.29 (s, 2H); 5.34 (s, 2H); 5.70 (m, 1H); 5.93 (m, 1H).
Preparation embodiment 8:
2,3,5,6-tetrafluoro-4-propenyl benzyl-3-(3,3,3-three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 127)
In the flask of a 500ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 21.8g (0.1mol), 2,3,5,6-tetrafluoro-4-propenyl benzylalcohol 22.0g (0.1mol), 180ml toluene is loaded onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, with the 100g washing once, dilute hydrochloric acid with 100g 5% washs once again, uses the sodium hydrogen carbonate solution of 100g 5% to wash once, and last 100g water washs once again, collecting toluene layer is heated to 100 ℃ and purifies solvent toluene and obtain compound 127 weight 36.1g, content 96.5% under the 10mmHg negative pressure.The molecular formula of this compound: C 19H 17F 7O 2Molecular weight 410, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 3.22 (s, 2H); 4.93 (m, 2H); 5.34 (s, 2H); 5.70 (m, 1H); 5.93 (m, 1H); 6.30 (m, 1H).
Preparation embodiment 9:
2,3,5,6-tetrafluoro-4-acetylene oxy-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 130)
In the flask of a 500ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 21.8g (0.1mol), 2,3,5,6-tetrafluoro-4-second alkynyloxy group benzylalcohol 22.0g (0.1mol), 180ml toluene is loaded onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, with the 100g washing once, dilute hydrochloric acid with 100g 5% washs once again, uses the sodium hydrogen carbonate solution of 100g 5% to wash once, and last 100g water washs once again, collecting toluene layer is heated to 100 ℃ and purifies solvent toluene and obtain compound 130 weight 36.7g, content 97.4% under the 10mmHg negative pressure.The molecular formula of this compound: C 18H 13F 7O 3Molecular weight 410, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 1.80 (s, 1H); 5.34 (s, 2H); 5.70 (m, 1H); 5.93 (m, 1H).
Preparation embodiment 10:
2,3,5,6-tetrafluoro-4-acetylene oxygen methyl-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 135)
In the flask of a 500ml, drop into 3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid 21.8g (0.1mol), 2,3,5,6-tetrafluoro-4-4-acetylene oxygen xylyl alcohol 23.4g (0.1mol), 180ml toluene is loaded onto water trap, add the 0.1g tosic acid again, be heated to backflow, band water reaction 6 hours, the complete room temperature that is cooled to of 20ml toluene reaction is added in the centre, with the 100g washing once, dilute hydrochloric acid with 100g 5% washs once again, uses the sodium hydrogen carbonate solution of 100g 5% to wash once, and last 100g water washs once again, collecting toluene layer is heated to 100 ℃ and purifies solvent toluene and obtain compound 135 weight 39.5g, content 96.3% under the 10mmHg negative pressure.The molecular formula of this compound: C 19H 15F 7O 3Molecular weight 424, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.51 (m, 1H); 1.30 (s, 1H); 4.79 (s, 2H); 5.34 (s, 2H); 5.70 (m, 1H); 5.93 (m, 1H).
Preparation embodiment 11:
2,3,5,6-tetrafluoro-4-acetylene oxygen methyl-benzyl-1R, trans-3-(3,3,3-three fluoro-1-propenyl)-2, the preparation of 2-dimethyl cyclopropane carboxylic acid ester (compound 136)
In the flask of a 500ml, drop into 1R, trans-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid acyl chlorides 23.5g (0.1mol), 2,3,5,6-tetrafluoro-4-4-acetylene oxygen xylyl alcohol 23.4g (0.1mol), 180ml toluene, 60 ℃ of following insulation reaction 4 hours, reaction is finished and is cooled to room temperature, with the 100g washing once, dilute hydrochloric acid with 100g 5% washs once again, uses the sodium hydrogen carbonate solution of 100g 5% to wash once, and last 100g water washs once again, collecting toluene layer is heated to 100 ℃ and purifies solvent toluene and obtain compound 136 weight 41.5g, content 98.3% under the 10mmHg negative pressure.The molecular formula of this compound: C 19H 15F 7O 3Molecular weight 424, and nuclear magnetic resonance spectrum (1H (ppm) CDCl3) 1.11 (s, 6H); 1.06 (m, 1H); 1.50 (m, 1H); 1.30 (s, 1H); 4.79 (s, 2H); 5.34 (s, 2H); 5.70 (m, 1H); 5.93 (m, 1H).Specific rotation α=+ 33 degree.
Preparation embodiment 12:
Be prepared as follows 2,3,5 of structure with reference to previous reaction, 6-tetrafluoro-4-acetylene oxygen methyl-benzyl-3-ethene-2,2-dimethyl cyclopropane carboxylic acid ester is compound in contrast
Below be example of formulations, if no special instructions, said part is weight part.
Example of formulations 1
The compounds of this invention 1 with preparation more than 20 parts, 75,76,86,109,120,127,130,135, in 136 any is dissolved in and adds 15 parts D80 solvent oil (Exxon Mobil petrochemical corporation (complex), 206 ℃～243 ℃ of boiling points) in the solution of 65 parts of dimethylbenzene, and fully mixes to obtain described mixture emulsifiable concentrate.
Example of formulations 2
The compounds of this invention 1 with preparation more than 5 parts, 75,76,86,109,120,127, in 130,135,136 any, 3 parts of synthetic hydrated silica fine powders, 0.3 part of PAP (mixture of phosphoric acid one isopropyl ester and diisopropyl phosphate) and 91.7 part of 300 talcous mixture of purpose stir to obtain pulvis with the juice agitator.
Example of formulations 3
Any solution that is dissolved in 10 parts of methylene dichloride in the The compounds of this invention 1,75,76,86,109,120,127,130,135,136 of preparation more than 0.1 part is mixed with 89.9 parts of deodorized kerosines, to obtain a kind of oily solution.
Example of formulations 4
With in 1 part of The compounds of this invention 109,120,127,130,135,136 any, the mixing solutions of 5 parts of methylene dichloride and 34 parts of deodorized kerosines is filled in the aerosol container.Valve is connected on the container and by this valve under 4 normal atmosphere, 60 parts of propelling agents (third butane) is filled in the container, to obtain a kind of aerosol.
Example of formulations 5
With 0.6 part of The compounds of this invention 109,120,127,130, mixing solutions and 50 parts of water of in 135,136 any, 5 parts of dimethylbenzene, 3.4 parts of deodorized kerosines and 1 part of Atmos 300 (emulsifying agent, the product of Atlas chemical company (Atlas ChemicalCo.)) are filled in the aerosol container.Then valve is connected to container and under 4 normal atmosphere, 40 parts of propelling agents (liquefied petroleum gas (LPG)) is fed in the container, to obtain water-borne aerosol by this valve.
Example of formulations 6
With 0.3g The compounds of this invention 75,86,109,120,127,130, the solution that in 135,136 any is dissolved in 20ml acetone mixes in order to the preparation mosquito-repellent incense equably with 99.7g base material (W-Gum, pyrethrum marc and wood powder are in the mixture of 4: 3: 3 ratios).Add 100ml water in mixture, and the mixture that obtains is fully kneaded, plastotype is also dry then, to obtain mosquito-repellent incense.
Example of formulations 7
Acetone is joined 0.8g The compounds of this invention 76,86,109,120, in the mixture of any in 127,130,135,136 and 0.4g piperonyl butoxide, prepare 10ml solution.Flood base material (a kind of fiberboard that compresses paper pulp and velveteen mixture: 2.5cm * 1.5cm, 0.3cm thickness) equably with the above-mentioned solution of 0.5ml, to obtain the electrically heated anti-mosquito incense sheet.
Example of formulations 8
Any solution that is dissolved in 97 parts of deodorized kerosines in 3 parts of The compounds of this invention 120,127,130,135 is filled in the container that polyvinyl chloride makes.Insert the absorbent core that inorganic powder is made in container, with the part of the electrically heated device for fumigation that obtains to absorb core pattern, described inorganic powder solidifies calcining then with tackiness agent, and heater heats can be used in the top of wherein said core.
Example of formulations 9
Be dissolved in the solution impregnation porous ceramic plate (4.0cm * 4.0cm, 1.2cm thickness) of proper amount of acetone with in the 100mg The compounds of this invention 120,127,130,135 any, to obtain the heating fumigating agent.
Example of formulations 10
Any solution that is dissolved in proper amount of acetone in the 1mg The compounds of this invention 120,127,130,135 evenly is administered on the filter paper bar (2.0cm * 2.0cm, 0.3mm thickness).Then acetone is vapored away, with the volatilizer that obtains to use under the room temperature.
Following check embodiment shows that pyrethroid compound of the present invention is effective as pest control agent.
Test implementation example 1
Add the water of 120 weight parts and mediate in the mixture of W-Gum, carbon dust and the wood powder (1: 5: 4) of 99.96 weight parts and be shaped, oven dry forms mosquito-repellent incense base material (diameter 12.0cm, thick 4mm, a counterweight 40g) then.
On the other hand, the 0.4w/v% solution of preparation compound 109 in kerosene.
On this cover incense coil base material, evenly spray the above-mentioned solution of 4ml, at room temperature place then and dried in 3 hours to obtain the mosquito-repellent incense W1 that a cover has 0.04w/w% The compounds of this invention 109 with micro-syringe.
Similarly, the 0.4w/v% solution of preparation compound 120 in kerosene obtains the mosquito-repellent incense W2 that a cover has 0.04w/w% compound 120;
The 0.4w/v% solution of preparation compound 127 in kerosene obtains the mosquito-repellent incense W3 that a cover has 0.04w/w% compound 127;
The 0.4w/v% solution of preparation compound 130 in kerosene obtains the mosquito-repellent incense W4 that a cover has 0.04w/w% compound 130;
The 0.4w/v% solution of preparation compound 136 in kerosene obtains the mosquito-repellent incense W5 that a cover has 0.04w/w% compound 136;
The 0.4w/v% solution of preparation control compound in kerosene obtains the mosquito-repellent incense W6 that a cover has the 0.04w/w% control compound;
The mosquito-repellent incense of W1-W6 is carried out kill mosquito evaluation of pesticide effectiveness contrast with reference to GB13917.4-92, and the examination worm is a culex pipiens pollens, and 2～3 days female mosquitos of not sucking blood in back sprout wings; Detailed process is to draw 20 examination mosquitos with mosquito sucking tube, puts into airtight drum test set, appoints and gets one section of tested mosquito-repellent incense, puts to fragrant frame, lights timing, removes mosquito-repellent incense behind the 1min, writes down down and out examination mosquito number at set intervals, and experimental result sees Table 3:
The comparison of table 3. The compounds of this invention and control compounds effect exterminating mosquito
Mosquito-repellent incense Effective constituent Concentration w/w% KT50(min)
Mosquito-repellent incense W1 Compound 109 0.04 7.1
Mosquito-repellent incense W2 Compound 120 0.04 6.3
Mosquito-repellent incense W3 Compound 127 0.04 4.1
Mosquito-repellent incense W4 Compound 130 0.04 4.3
Mosquito-repellent incense W5 Compound 136 0.04 3.9
Mosquito-repellent incense W6 Control compound 0.04 To no effect
Test implementation example 2
Kerosene with 0.3 weight part compound 130 and 59.7 weight parts under heating mixes a kind of pesticide preparation of preparation.The preparation that obtains is put into the aerosol jar, on jar a valve is housed, and inject 40.0 weight parts, third butane adding to depress,, wherein contain compound 130 and be 0.3w/w% to obtain a kind of insect aerosol by this valve.
This insect aerosol is carried out mosquito according to GB13917.2-92, fly, the efficacy testing of Groton bug adopts airtight drum device.Detailed process is as follows: will put into cylinder for the examination insect; after waiting to try worm recovery normal activity; metered injection 1g medicament from the insect aerosol jar; extracting baffle plate behind the 1min out makes the examination worm contact with medicament; down and out examination borer population is write down in timing immediately, and opening entry at regular intervals; to all be transferred in the dependent insect cage of cleaning behind the 20min, check dead examination borer population behind the 24h for the examination worm.Wherein Groton bug is checked the 72h mortality ratio.The results are shown in Table 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 6.3 minute 100％
Fly 5.9 minute 100％
Groton bug 7.0 minute 95％(72h)
The result shows: the aerosol of The compounds of this invention 130 preparations is to mosquito, and fly, Groton bug have good insect killing effect.
Test implementation example 3
With the carmine spider mite is the activity of killing of 1,75,86 pairs of acarids of examination worm test The compounds of this invention.The examination worm: carmine spider mite (Tetrangychus cinnabarinus), for trying temperature: 26 ± 1 ℃; Humidity: 70 ± 10%; Testing method: adopt pickling process, after adult is connected leaf of Broadbean flood 5 seconds in the soup that with the methyl-sulphoxide is solvent, blade is inserted in the bottle, 3 repetitions are established in every processing, check dead borer population after 24 hours, the calculating mortality ratio.Test result is as shown in table 5.
Table 5. The compounds of this invention is to the killing effect of carmine spider mite

Claims (10)

1. ester cpds with insecticidal activity, its structure be as shown in the formula shown in (I) or the formula (II),
Wherein,
Z1 is hydrogen atom, cyano group, ethynyl or nitro;
R1 is hydrogen atom, cyano group, halogen atom, hydroxyl, nitro, amido, C1-C4 alkyl or halo alkyl or group-(CH 2) m-X-R1 ', m=0 or 1 wherein, X is Sauerstoffatom or sulphur atom, R1 ' is C1-C4 alkyl or halo alkyl; X1 is unsaturated alkyl or the halo alkyl of cyano group, a methyl fluoride, difluoromethyl, C2-C4;
Figure F2010100026785C00012
Wherein,
Z2 is hydrogen atom, cyano group, ethynyl or nitro;
N is the integer of 1-4;
R2 is cyano group, halogen atom, hydroxyl, nitro, amido, halogenated methyl, C2-C4 alkyl or halo alkyl or group-(CH 2) q-X2-R2 ', q=0 or 1 wherein, X2 is Sauerstoffatom or sulphur atom, R2 ' is halogenated methyl, C2-C4 alkyl or halo alkyl.
2. the described ester cpds of claim 1, it is characterized in that: described compound is any one three-dimensional chemical isomer of compound shown in formula (I) or the formula (II).
3. the described ester cpds of claim 1, it is characterized in that: described compound is the mixture of the different isomerization body of compound shown in formula (I) or the formula (II).
4. the described ester cpds of claim 1 is characterized in that, it is selected from following compound:
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(3,3-two fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure F2010100026785C00021
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(3-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure F2010100026785C00022
2,3,5,6-tetrafluoro-4-propenyl-alpha-cyano benzyl-3-(2-cyano group-1-vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure F2010100026785C00023
2,3,4,5,6-PFBBR-3-(2-ethynyl-1-vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
2,3,5,6-tetrafluoro-4-propenyl benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure F2010100026785C00031
2,3,5,6-tetrafluoro-4-proyl benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
2,3,4,5,6-PFBBR-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
2,3,5,6-tetrafluoro-4-acetylene oxy-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure F2010100026785C00034
Perhaps
2,3,5,6-tetrafluoro-4-acetylene oxygen methyl-benzyl-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester, structure is:
Figure F2010100026785C00041
5. the described ester cpds of claim 1 is characterized in that, it is selected from a kind of in the following compound:
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-Z-(1R, trans)-3-(3,3-two fluoro-1-propenyl)-2,2-dimethylcyclopropane carboxylic;
2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-Z-(1R, trans)-3-(3-fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
2,3,5,6-tetrafluoro-4-proyl benzyl-Z-(1R, trans)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
2,3,5,6-tetrafluoro-4-acetylene oxy-benzyl-Z-(1R, trans)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester; Perhaps
2,3,5,6-tetrafluoro-4-acetylene oxygen methyl-benzyl-Z-(1R, trans)-3-(3,3,3-three fluoro-1-propenyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
6. the preparation method of the described ester cpds of claim 1 is characterized in that, the synthetic method of the compound shown in the described formula (I) is as follows:
By the acid shown in the pure and mild formula (B) shown in the formula (A) according to 0.8～1.2: 1 mol ratio, in organic solvent, under 60-130 ℃, sulfuric acid or Catalyzed by p-Toluenesulfonic Acid, carry out esterification and obtain; Wherein, the mol ratio of the alcohol shown in catalyst sulfuric acid or tosic acid and the formula (A) is 0.01～0.1: 1; Perhaps
, made with the pure esterification reaction shown in the formula (A) after the chloride reagent chloride obtains the acyl chlorides shown in the formula (C) by the acid shown in the formula (B), wherein the mol ratio of the acyl chlorides shown in the pure and mild formula (C) shown in (A) is 0.8～1.2: 1 again;
Figure F2010100026785C00042
Wherein, Z1 is hydrogen atom, cyano group, ethynyl or nitro; R1 is hydrogen atom, cyano group, halogen atom, hydroxyl, nitro, amido, C1-C4 alkyl or halo alkyl or group-(CH 2) m-X-R1 ', m=0 or 1 wherein, X is Sauerstoffatom or sulphur atom, R1 ' is C1-C4 alkyl or halo alkyl;
Figure F2010100026785C00051
Wherein X1 is unsaturated alkyl or the halo alkyl of cyano group, a methyl fluoride, difluoromethyl or C2-C4;
Figure F2010100026785C00052
Wherein X1 is unsaturated alkyl or the halo alkyl of cyano group, a methyl fluoride, difluoromethyl, C2-C4.
7. the preparation method of the described ester cpds of claim 1 is characterized in that, the synthetic method of the compound shown in the described formula (II) is as follows:
By the acid shown in the pure and mild formula (E) shown in the formula (D) according to 0.8～1.2: 1 mol ratio, in organic solvent, under 60-130 ℃, sulfuric acid or Catalyzed by p-Toluenesulfonic Acid, carry out esterification and obtain; Wherein, the mol ratio of the alcohol shown in catalyst sulfuric acid or tosic acid and the formula (D) is 0.01～0.1: 1; Perhaps
, made with the pure esterification reaction shown in the formula (D) after the chloride reagent chloride obtains the acyl chlorides shown in the formula (F) by the acid shown in the formula (E), wherein the mol ratio of the acyl chlorides shown in the pure and mild formula (F) shown in (D) is 0.8～1.2: 1 again;
Figure F2010100026785C00053
Wherein, Z2 is hydrogen atom, cyano group, ethynyl or nitro; N is the integer of 1-4; R2 is cyano group, halogen atom, hydroxyl, nitro, amido, halogenated methyl, C2-C4 alkyl or halo alkyl or group-(CH 2) q-X2-R2 ': q=0 or 1 wherein, X2 is Sauerstoffatom or sulphur atom, R2 ' is halogenated methyl, C2-C4 alkyl or halo alkyl;
Figure F2010100026785C00054
8. the described ester cpds of claim 1 is as the application of the pesticide active ingredient of pest control.
9. the described application of claim 8 is characterized in that: described insect is insect, nematode or the acarid of public health insect or harm agriculture production.
10. the described application of claim 9 is characterized in that: described public health insect is mosquito, fly or cockroach.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109651145A (en) * 2019-01-17 2019-04-19 江苏春江润田农化有限公司 The synthetic method of trifluoro ynoic acid methyl ester
TWI663151B (en) * 2016-05-31 2019-06-21 日商大日本除蟲菊股份有限公司 Ester compounds and use thereof
CN109907067A (en) * 2017-12-12 2019-06-21 江苏扬农化工股份有限公司 It can be used for the ester compounds of desinsection
WO2023160316A1 (en) * 2022-02-22 2023-08-31 江苏扬农化工股份有限公司 Pyrethroid compound containing double bonds and cyano groups, synthesis method therefor, and application thereof

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JP2018043961A (en) * 2016-09-16 2018-03-22 大日本除蟲菊株式会社 Ester compound and use therefor

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4868209A (en) * 1979-12-21 1989-09-19 Imperial Chemical Industries Plc Halogenated esters

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Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4868209A (en) * 1979-12-21 1989-09-19 Imperial Chemical Industries Plc Halogenated esters

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
TWI663151B (en) * 2016-05-31 2019-06-21 日商大日本除蟲菊股份有限公司 Ester compounds and use thereof
CN109907067A (en) * 2017-12-12 2019-06-21 江苏扬农化工股份有限公司 It can be used for the ester compounds of desinsection
CN109651145A (en) * 2019-01-17 2019-04-19 江苏春江润田农化有限公司 The synthetic method of trifluoro ynoic acid methyl ester
WO2023160316A1 (en) * 2022-02-22 2023-08-31 江苏扬农化工股份有限公司 Pyrethroid compound containing double bonds and cyano groups, synthesis method therefor, and application thereof

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