CN100545144C - A kind of optically active pyrethroid coumpound and its production and application - Google Patents
A kind of optically active pyrethroid coumpound and its production and application Download PDFInfo
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- CN100545144C CN100545144C CNB2008101326120A CN200810132612A CN100545144C CN 100545144 C CN100545144 C CN 100545144C CN B2008101326120 A CNB2008101326120 A CN B2008101326120A CN 200810132612 A CN200810132612 A CN 200810132612A CN 100545144 C CN100545144 C CN 100545144C
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
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- 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
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Abstract
The invention provides the pyrethroid coumpound of a kind of structure: (A) R wherein as shown in the formula A
1And R
2It is respectively halogen identical or inequality.Described compound compared with prior art has higher insecticidal effect.The present invention also provides the preparation method and the application aspect the control sanitary insect pest of described compound.
Description
Technical field
The present invention relates to a kind of pyrethroid coumpound, especially a kind of optically active pyrethroid coumpound and safety thereof, the preparation method of high yield and application.
Background technology
Pyrethroid coumpound can be used to prevent and treat mosquito, and has higher insecticidal activity, and this is widely known by the people, and U.S. Pat 4370346 has been introduced R in the compound of general molecular formula (A)
1And R
2Racemoid during simultaneously for chlorine can be used as a class pest controllers, can prepare sterilant and also addressed this racemoid among Chinese patent CN1669429, the CN1669419.Yet we find to have higher insecticidal activity through the single optical isomer that split in research process, and through further exploring, we find to work as R
1And R
2During for chlorine or bromine identical or inequality, the compound of the single optical activity that structural formula A represents all has very high insecticidal activity.Along with people are more and more higher to environmental protection requirement; the high biological activity body of agricultural chemicals more and more causes people's attention; pyrethroid has 2～8 optical isomers usually, and biological activity is widely different between each isomer, therefore needs the most highly active isomer of research preparation.From the angle of environmental protection, use highly active single optical 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.
Purpose of the present invention just provides a kind of new pyrethroid coumpound, and this compound is the single optical activity body, and the present invention simultaneously also provides a kind of synthetic method and the application of this compound.
Summary of the invention
The objective of the invention is to: provide a kind of pyrethroid compound to have the pyrethroid compound of higher insecticidal effect than prior art.
Purpose of the present invention is achieved through the following technical solutions:
A kind of pyrethroid compound is provided, and its structure is suc as formula A:
R wherein
1And R
2It is respectively halogen identical or inequality.
In the described compound, the R of preferred compound
1And R
2Be respectively fluorine, chlorine or bromine identical or inequality; Wherein further preferred following compound:
Compound I: R
1And R
2Be chlorine simultaneously, this compound is 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester;
Compound I I:R
1And R
2Be bromine simultaneously, this compound is 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester;
Compound III: R
1And R
2Be fluorine simultaneously, this compound is 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2,2-difluoroethylene base)-2,2-dimethyl cyclopropane carboxylic acid ester; Perhaps
Compound IV: R
1Be chlorine and R
2Be bromine, this compound is 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2-chloro-2-bromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
The present invention also provides the preparation method of described compound, may further comprise the steps:
1) utilize chemical resolving agent to split the racemization trans-chrysanthemate, obtain corresponding dextrorotation trans-chrysanthemate, wherein, described racemization trans-chrysanthemate is the compound of structure as shown in the formula B, R
1And R
2It is respectively halogen identical or inequality; The mol ratio of described chemical resolving agent and racemization trans-chrysanthemate is 0.2: 1～4: 1;
2) with chloride reagent with the dextrorotation trans-chrysanthemate chloride that step 1) obtains, obtain the trans acyl chlorides of corresponding dextrorotation; Wherein, the mol ratio of described chloride reagent and dextrorotation trans-chrysanthemate is 0.2: 1～4: 1; Described chloride reagent can be selected from a kind of in phosphorus trichloride, sulfur oxychloride, carbonic acid two (three chloromethanes) ester;
3) with step 2) the trans acyl chlorides of dextrorotation and 2,3,5 that obtains, 6-tetrafluoro-4-methoxyl methyl phenylcarbinol carries out esterification, obtains the pyrethroid compound that described structure is formula A; Wherein, the trans acyl chlorides of described dextrorotation and 2,3,5, the mol ratio of 6-tetrafluoro-4-methoxyl methyl phenylcarbinol is 0.2: 1～4: 1.
Wherein, the described chemical resolving agent of step 1) is dextral chirality organic amine compound, can be selected from a kind of in the mould amine of dextrorotation chlorine ((+) N, N-dimethyl-p-nitrophenyl-1, ammediol), dextrorotation PTE ((+) β-p-methylphenyl-α-Ben Yian) or the dextrorotation α-Ben Yian.
The present invention also provides the application of described compound in the control sanitary insect pest.
In the described application, sanitary insect pest is mosquito, fly or Groton bug etc.
Compared with prior art, the present invention has following beneficial effect:
Preparation method's quality height of this compound provided by the invention, yield height, process safely, be easy to control.
2. the biological efficacy test result shows, compound of the present invention has remarkable prevention effect to housefly, culex pipiens pollens, culex pipiens fatigans, Groton bug etc., the insecticidal activity of its optically active isomer is far above similar raceme, carry out efficacy testing with hygienic insecticide esbiothrin commonly used at present in addition, the result shows that the drug effect of this compounds is at more than 20 times of esbiothrin.As replacing esbiothrin with this compounds, reach same effect, its dosage only needs about 5% of esbiothrin, has alleviated the pollution to environment greatly.
Embodiment
With some concrete examples the present invention is described below, but the present invention not only is confined to following embodiment:
Preparation embodiment 1: trans 2, the fractionation of 2-dimethyl-3-(2, the 2-dichloroethylene) cyclopropane-carboxylic acids (trans dichlor chrysanthemic acid)
In the four-hole bottle of a 1000ml, drop into trans dichlor chrysanthemic acid 100.0g, the mould amine 100.0g of dextrorotation chlorine is dissolved in 500ml toluene, throws to finish and stirs, be warming up to 110 ℃ of back flow reaction 1 hour, at 3 hours internal cooling to 40 ℃, be incubated 1 hour then, again at 2 hours internal cooling to 10 ℃, be incubated 0.5 hour, have a large amount of crystal to separate out this moment.Filter, in the mother liquor that obtains, add the hcl acidifying of 100g10% to pH 2～3, layering, oil-reservoir water is washed till nearly neutrality, be heated to 100 ℃ and purify solvent toluene under the 10mmHg negative pressure, obtain (R)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane-carboxylic acid 46.5g, the effective body ee of dextrorotation value 97%.
Preparation embodiment 2: the fractionation of trans dichlor chrysanthemic acid
In the four-hole bottle of a 1000ml, drop into trans dichlor chrysanthemic acid 100.0g, dextrorotation PTE 125.0g, be dissolved in 400ml toluene, throw to finish stir, be warming up to 110 ℃ of back flow reaction 1 hour, then at 3 hours internal cooling to 60 ℃, be incubated 1 hour, at 2 hours internal cooling to 20 ℃, be incubated 1 hour again, have a large amount of crystal to separate out this moment, filtration obtains crystal, the hcl acidifying that adds 200g 5% adds the extraction of 400ml toluene, layering simultaneously, oil-reservoir water is washed till nearly neutrality, be heated to 100 ℃ and purify solvent toluene under the 10mmHg negative pressure, obtain (R)-2,2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane-carboxylic acid 45.2g, the effective body ee of dextrorotation value 96%.
Preparation embodiment 3: the chloride of the trans dichlor chrysanthemic acid of dextrorotation
In the four-hole bottle of a 1000ml, drop into the trans dichlor chrysanthemic acid 209g of dextrorotation (1molee value 97%) of preparation embodiment 1, be dissolved in 600ml toluene, throw to finish and stir, be warming up to 50 ℃, drip SOCl
2142g (1.2mol) drips in 2 hours and finishes, and is warming up to 60 ℃ again, insulation reaction.Reaction is finished be heated to 80 ℃ of desolventizing toluene under the 30mmHg negative pressure, and 60 ℃～75 ℃ cuts are received in rectifying under the 10mmHg negative pressure again, obtaining (R)-2,2-dimethyl-3-is trans-(2, the 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid 216.1g, yield 95.1%, the effective body ee of dextrorotation value 97%.
Preparation embodiment 4: the chloride of the trans dichlor chrysanthemic acid of dextrorotation
In the four-hole bottle of a 1000ml, drop into the trans dichlor chrysanthemic acid 209g of dextrorotation (1molee value 97%) of preparation embodiment 1, be dissolved in 600ml toluene, throw to finish and stir, be warming up to 50 ℃, drip the toluene solution 200ml that contains triphosgene 118.7g (0.4mol), drip in 2 hours and finish, be warming up to 60 ℃ again, insulation reaction.Reaction is finished be heated to 80 ℃ of desolventizing toluene under the 30mmHg negative pressure, and 60 ℃～75 ℃ cuts are received in rectifying under the 10mmHg negative pressure again, obtaining (R)-2,2-dimethyl-3-is trans-(2, the 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid 214.1g, yield 94.3%, the effective body ee of dextrorotation value 97%.
Preparation embodiment 5: trans 2, the fractionation of 2-dimethyl-3-(2, the 2-dibromo vinyl) cyclopropane-carboxylic acids (trans dibromo chrysanthemic acid)
In the four-hole bottle of a 1000ml, drop into trans dibromo chrysanthemic acid 100.0g, the mould amine 80.0g of dextrorotation chlorine is dissolved in 500ml toluene, throws to finish and stirs, be warming up to 110 ℃ of back flow reaction 1 hour, at 3 hours internal cooling to 40 ℃, be incubated 1 hour then, again at 2 hours internal cooling to 10 ℃, be incubated 0.5 hour, have a large amount of crystal to separate out this moment.Filter, in the mother liquor that obtains, add the hcl acidifying of 100g10% to pH 2～3, layering, oil-reservoir water is washed till nearly neutrality, be heated to 100 ℃ and purify solvent toluene under the 10mmHg negative pressure, obtain (R)-2,2-dimethyl-3-trans-(2, the 2-dibromo vinyl) cyclopropane-carboxylic acid 44.7g, the effective body ee of dextrorotation value 95%.
Preparation embodiment 6: the chloride of the trans dibromo chrysanthemic acid of dextrorotation
In the four-hole bottle of a 1000ml, drop into the trans dibromo chrysanthemic acid 298g of dextrorotation (1molee value 95%) of preparation embodiment 5, be dissolved in 600ml toluene, throw to finish and stir, be warming up to 50 ℃, drip SOCl
2142g (1.2mol) drips in 2 hours and finishes, and is warming up to 60 ℃ again, insulation reaction.Reaction is finished be heated to 80 ℃ of desolventizing toluene under the 30mmHg negative pressure, and 60 ℃～75 ℃ cuts are received in rectifying under the 10mmHg negative pressure again, obtaining (R)-2,2-dimethyl-3-is trans-(2, the 2-dibromo vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 305.4g, yield 94.7%, the effective body ee of dextrorotation value 95%.
Preparation embodiment 7: trans 2, the fractionation of 2-dimethyl-3-(2,2-difluoroethylene base) cyclopropane-carboxylic acids (trans difluoro chrysanthemumic acid)
In the four-hole bottle of a 1000ml, drop into trans difluoro chrysanthemumic acid 100.0g, the mould amine 120.0g of dextrorotation chlorine is dissolved in 500ml toluene, throws to finish and stirs, be warming up to 110 ℃ of back flow reaction 1 hour, at 3 hours internal cooling to 40 ℃, be incubated 1 hour then, again at 2 hours internal cooling to 10 ℃, be incubated 0.5 hour, have a large amount of crystal to separate out this moment.Filter, in the mother liquor that obtains, add the hcl acidifying of 100g10% to pH 2～3, layering, oil-reservoir water is washed till nearly neutrality, be heated to 100 ℃ and purify solvent toluene under the 10mmHg negative pressure, obtain (R)-2,2-dimethyl-3-trans-(2,2-difluoroethylene base) cyclopropane-carboxylic acid 45.2g, the effective body ee of dextrorotation value 96%.
Preparation embodiment 8: the chloride of the trans difluoro chrysanthemumic acid of dextrorotation
In the four-hole bottle of a 1000ml, drop into the trans difluoro chrysanthemumic acid of the dextrorotation 176g (1molee value 96%) of preparation embodiment 7, be dissolved in 600ml toluene, throw to finish and stir, be warming up to 50 ℃, drip SOCl
2142g (1.2mol) drips in 2 hours and finishes, and is warming up to 60 ℃ again, insulation reaction.Reaction is finished be heated to 80 ℃ of desolventizing toluene under the 30mmHg negative pressure, and 60 ℃～75 ℃ cuts are received in rectifying under the 10mmHg negative pressure again, obtaining (R)-2,2-dimethyl-3-is trans-(2,2-difluoroethylene base) cyclopropane carboxylic acid isoxazolecarboxylic acid 180.1g, yield 93.3%, the effective body ee of dextrorotation value 96%.
Preparation embodiment 9: trans 2, the fractionation of 2-dimethyl-3-(2-chloro-2-bromo vinyl) cyclopropane-carboxylic acid
In the four-hole bottle of a 1000ml, drop into trans 2,2-dimethyl-3-(2-chloro-2-bromo vinyl) cyclopropane-carboxylic acid 100.0g, the mould amine 90.0g of dextrorotation chlorine, be dissolved in 500ml toluene, throw to finish stir, be warming up to 110 ℃ of back flow reaction 1 hour, then at 3 hours internal cooling to 40 ℃, be incubated 1 hour, at 2 hours internal cooling to 10 ℃, be incubated 0.5 hour again, have a large amount of crystal to separate out this moment.Filter, in the mother liquor that obtains, add the hcl acidifying of 100g10% to pH 2～3, layering, oil-reservoir water is washed till nearly neutrality, under the 10mmHg negative pressure, be heated to 100 ℃ and purify solvent toluene, obtaining (R)-2,2-dimethyl-3-is trans-(2-chloro-2-bromo vinyl) cyclopropane-carboxylic acid 44.9g, the effective body ee of dextrorotation value 95%.
Preparation embodiment 10: dextrorotation is trans 2, the chloride of 2-dimethyl-3-(2-chloro-2-bromo vinyl) cyclopropane-carboxylic acid
In the four-hole bottle of a 1000ml, drop into (R)-2 of preparation embodiment 9,2-dimethyl-3-is trans-(2-chloro-2-bromo vinyl) cyclopropane-carboxylic acid 253.5 (1molee value 95%), be dissolved in 600ml toluene, throw to finish and stir, be warming up to 50 ℃, dropping 8OCl
2142g (1.2mol) drips in 2 hours and finishes, and is warming up to 60 ℃ again, insulation reaction.Reaction is finished be heated to 80 ℃ of desolventizing toluene under the 30mmHg negative pressure, and 60 ℃～75 ℃ cuts are received in rectifying under the 10mmHg negative pressure again, obtain (R)-2,2-dimethyl-3-is trans-(2-chloro-2-bromo vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 258.6g, and yield 94.2%, the effective body ee of dextrorotation value 95%.
Preparation embodiment 11:2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester (Compound I) synthetic
In the four-hole bottle of a 2000ml, drop into tetrafluoro to methoxyl methyl phenylcarbinol 112.0g, pyridine 50.0g, be dissolved in 800ml toluene, throw to finish and stir, 0～5 ℃ of (R)-2 that drip preparation embodiment 3 preparations down, 2-dimethyl-3-trans-(2, the 2-dichloroethylene) cyclopropane carboxylic acid isoxazolecarboxylic acid 114.0g drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 400ml 5% salt acid elution, with 400ml 5%NaHCO3 washing, divide oil-yielding stratum under the 10mmHg negative pressure, to be heated to 100 ℃ and purify solvent toluene again, obtain compound 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester faint yellow solid, weight 203.3g, content is 97.8%, yield 95.8%.The molecular formula of this compound: C
17H
17C
12F
4O
3Molecular weight: 416.2 optically-actives [α]=-9.32 dissolve in organic solvents such as toluene, benzene, dimethylbenzene, and the infrared signature absorption peak is 3020,2950,2840,1750,1640,1580,1240,1050cm
-1Nuclear magnetic resonance spectrum (1H (ppm) CDCl
3) 1.11 (m, 6H); 1.06-1.41 (m, 2H); 3.24 (s, 3H); 4.63 (m, 2H); 5.34 (m, 2H); 5.63 (d, 1H).
Preparation embodiment 12:2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester (Compound I I) synthetic
56.0g tetrafluoro drops in the 1000ml four-hole bottle methoxyl methyl phenylcarbinol, pyridine 25g, 400ml toluene, throwing Bi Changwen stirred 15 minutes down, 0～5 ℃ of (R)-2 that drip preparation embodiment 6 preparations down, 2-dimethyl-3-trans-(2, the 2-dibromo vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 79.4g, drip complete 10 ℃ and be incubated 1 hour down, oil reservoir is used 100ml 5%NaHCO again with 150ml 5% salt acid elution
3Washing is washed to neutrality again.Oil reservoir negative pressure piptonychia benzene, temperature is 100 ℃ eventually, and absolute pressure 10mmHg obtains compound 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester is a pale solid, and weight 125.1g, content are 97.1%, and yield is 96.2%.The molecular formula of this compound: C
17H
17Br
2F
4O
3Molecular weight: 505.1 optically-actives [α]=-7.63 dissolve in organic solvents such as toluene, benzene, dimethylbenzene, and the infrared signature absorption peak is 3020,2940,2840,1750,1630,1580,1240 for the infrared signature absorption peak, 1040cm
-1Nuclear magnetic resonance spectrum (1H (ppm) CDCl
3) 1.11 (m, 6H); 1.06-1.41 (m, 2H); 3.24 (s, 3H); 4.63 (m, 2H); 5.34 (m, 2H); 6.32 (d, 1H).
Preparation embodiment 13:2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2,2-difluoroethylene base)-2,2-dimethyl cyclopropane carboxylic acid ester (compound III) synthetic
In the four-hole bottle of a 2000ml, drop into tetrafluoro to methoxyl methyl phenylcarbinol 112.0g, pyridine 50.0g, be dissolved in 800ml toluene, throw to finish and stir, 0～5 ℃ of (R)-2 that drip preparation embodiment 8 preparations down, 2-dimethyl-3-trans-(2,2-difluoroethylene base) cyclopropane carboxylic acid isoxazolecarboxylic acid 97.5g drips 20 ℃ of reactions of Bi Shengzhi 4 hours.With 300ml 5% salt acid elution, use 300ml 5%NaHCO again
3Washing, oil reservoir is heated to 100 ℃ and purifies solvent toluene under the 10mmHg negative pressure, obtain compound 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2,2-difluoroethylene base)-2,2-dimethyl cyclopropane carboxylic acid ester faint yellow solid, weight 196.3g, content are 96.9%, yield 93.8%.The molecular formula of this compound: C
17H
17F
6O
3Molecular weight: 383.2 optically-actives [α]=-4.51, infrared signature absorption peak are 3010,2950,2840,1750,1640,1580,1240,1050cm
-1Nuclear magnetic resonance spectrum (1H (ppm) CDCl
3) 1.11 (m6H); 1.06-1.41 (m, 2H); 3.24 (s, 3H); 4.63 (m, 2H); 5.34 (m, 2H); 4.72 (d, 1H).
Preparation embodiment 14:2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2-chloro-2-bromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester (compound IV) synthetic
Tetrafluoro drops in the four-hole bottle of 2000ml methoxyl methyl phenylcarbinol 112.0g, pyridine 50.0g, 800ml toluene, stirring and dissolving, under 0～5 ℃ to (the R)-2-chloro-2-bromo-3-that wherein drips preparation embodiment 10 preparations trans-(2-chloro-2-bromo vinyl) cyclopropane carboxylic acid isoxazolecarboxylic acid 136.2g, drip and finish, 10 ℃ of insulation reaction 4 hours, use 5% chlorohydric acid pickling, 5%NaHCO
3The solution alkali cleaning is carried out twice washing with oil reservoir with ionized water 200ml again.Oil reservoir negative pressure piptonychia benzene, temperature is 100 ℃ eventually, and absolute pressure 10mmHg obtains compound 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2-chloro-2-bromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester is a canescence look solid, and weight 229.8g, content are 98.2%, and yield is 98.1%.The molecular formula of compound: C
17H
17BrClF
4O
3Molecular weight 460.7, the infrared signature absorption peak is 3020,2950,2840,1760,1640,1580,1240 for the infrared signature absorption peak, 1050cm
-1Nuclear magnetic resonance spectrum (
1H (ppm) CDCl
31.11 (m, 6H); 1.06-1.41 (m, 2H); 3.24 (s, 3H); 4.63 (m, 2H); 5.34 (m, 2H); 6.05 (d, 1H).
Test implementation example 1
Compound I of the present invention, Compound I I, compound III and present the most frequently used d-allethrin are carried out evaluation of pesticide effectiveness contrast according to GB13917.4-92.Compound I 0.014g is dissolved in 1g kerosene, and drop to the blank mosquito-repellent incense blank of 35g is made 0.04% Compound I mosquito-repellent incense; Compound I I 0.014g is dissolved in 1g kerosene, and drop to the blank mosquito-repellent incense blank of 35g is made 0.04% Compound I I mosquito-repellent incense; Compound III 0.014g is dissolved in 1g kerosene, and drop to the blank mosquito-repellent incense blank of 35g is made 0.04% compound III mosquito-repellent incense; 0.28 being dissolved in the same drop of 1g kerosene to the blank mosquito-repellent incense blank of 35g, d-allethrin makes 0.8% dextrorotation propylene mosquito-repellent incense.Respectively four kinds of mosquito-repellent incenses are carried out efficacy testing, detailed process is to draw 20 female culex pipiens fatigans with mosquito sucking tube, put into airtight drum test set, appoint and get one section of tested mosquito-repellent incense, put to mosquito coil frame the igniting mosquito-repellent incense timing, remove mosquito-repellent incense behind the 1min, write down down and out examination mosquito number at set intervals, will all be transferred in the dependent insect cage of cleaning behind the 20min, check dead examination mosquito number behind the 24hr for the examination mosquito.The results are shown in Table 1:
The mosquito-proof effect of table 1. The compounds of this invention and d-allethrin relatively
| The mosquito-repellent incense type | Concentration (m/m) | KT50(min) | 24 hours mortality ratio |
| Compound I | 0.04％ | 4.32 | 100％ |
| Compound I I | 0.04％ | 7.23 | 100％ |
| Compound III | 0.04％ | 10.50 | 95％ |
| D-allethrin | 0.8％ | 4.17 | 95％ |
The result shows that the relative effectivenes of Compound I is at more than 20 times of d-allethrin, and the relative effectivenes of Compound I I is at more than 10 times of d-allethrin, and the relative effectivenes of compound III is at more than 3 times of d-allethrin.
Test implementation example 2
With Compound I of the present invention and compound (RS) 2,3,5,6-tetrafluoro-4-methoxyl methyl benzyl-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester (raceme that Compound I does not split) is made 0.08% mosquito-repellent incense respectively with embodiment 1 same method, carries out the evaluation of pesticide effectiveness according to GB13917.4-92, and the result is as shown in table 2:
The anti-civilian effect of table 2. single optical activity compound of the present invention and its raceme relatively
| The mosquito-repellent incense type | Concentration (m/m) | KT50(min) | 24 hours mortality ratio % |
| Compound I | 0.08％ | 3.43 | 100％ |
| The raceme of Compound I | 0.08％ | 5.80 | 100％ |
The result shows: the relative reactivity of Compound I is 1.7 times of raceme.
Claims (6)
1. pyrethroid compound, its structure are suc as formula A:
It is characterized in that: R
1And R
2It is respectively identical chlorine or bromine.
2. the described described compound of claim 1 is characterized in that: R
1And R
2Be chlorine simultaneously, this compound is 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dichloroethylene)-2,2-dimethyl cyclopropane carboxylic acid ester.
3. the described described compound of claim 1 is characterized in that: R
1And R
2Be bromine simultaneously, this compound is 2,3,5, and 6-tetrafluoro-4-methoxyl methyl benzyl (1R, 3S)-3-(2, the 2-dibromo vinyl)-2,2-dimethyl cyclopropane carboxylic acid ester.
4. the preparation method of the described compound of claim 1 may further comprise the steps:
1) utilize chemical resolving agent to split the trans chrysanthemumic acid of racemization, obtain the trans chrysanthemumic acid of corresponding dextrorotation, the trans chrysanthemumic acid of described dextrorotation is the compound of structure as shown in the formula B, wherein R
1And R
2It is respectively identical chlorine or bromine; Described chemical resolving agent is (+) N, N-dimethyl-p-nitrophenyl-1, and a kind of in ammediol, (+) β-p-methylphenyl-α-Ben Yian or the dextrorotation α-Ben Yian, the mol ratio of the chrysanthemumic acid that itself and racemization are trans is 0.2: 1～4: 1;
2) with chloride reagent with the trans chrysanthemumic acid chloride of dextrorotation that step 1) obtains, obtain the trans acyl chlorides of corresponding dextrorotation; Wherein, the mol ratio of the trans chrysanthemumic acid of described chloride reagent and dextrorotation is 0.2: 1～4: 1; Described chloride reagent is selected from a kind of in phosphorus trichloride, sulfur oxychloride, carbonic acid two (three chloromethanes) ester;
3) with step 2) the trans acyl chlorides and 2,3,5 of dextrorotation that obtains, 6-tetrafluoro-4-methoxyl methyl phenylcarbinol carries out esterification, obtains the pyrethroid compound that described structure is formula A; Wherein, the acyl chlorides that described dextrorotation is trans and 2,3,5, the mol ratio of 6-tetrafluoro-4-methoxyl methyl phenylcarbinol is 0.2: 1～4: 1.
5. the application of the described compound of claim 1 in the control sanitary insect pest.
6. the described application of claim 5, its feature exists: described sanitary insect pest is mosquito, fly or Groton bug.
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|---|---|---|---|
| CNB2008101326120A CN100545144C (en) | 2008-04-29 | 2008-07-07 | A kind of optically active pyrethroid coumpound and its production and application |
| MYPI2010006293A MY178016A (en) | 2008-04-29 | 2009-01-23 | An optically active pyrethroid compound and preparation process and use thereof |
| PCT/CN2009/070289 WO2009132526A1 (en) | 2008-04-29 | 2009-01-23 | An optically active pyrethroid compound and preparation process and use thereof |
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| CN200810094390 | 2008-04-29 | ||
| CNB2008101326120A CN100545144C (en) | 2008-04-29 | 2008-07-07 | A kind of optically active pyrethroid coumpound and its production and application |
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| CN100545144C true CN100545144C (en) | 2009-09-30 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102283240A (en) * | 2011-06-29 | 2011-12-21 | 贵阳柏丝特化工有限公司 | Pesticide composition |
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| CN100545144C (en) * | 2008-04-29 | 2009-09-30 | 江苏扬农化工股份有限公司 | A kind of optically active pyrethroid coumpound and its production and application |
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| JP2011116737A (en) * | 2009-10-30 | 2011-06-16 | Sumitomo Chemical Co Ltd | Harmful organism-controlling composition and method for controlling harmful organism |
| JP5589712B2 (en) * | 2009-10-30 | 2014-09-17 | 住友化学株式会社 | Pest control composition and pest control method |
| JP5589713B2 (en) * | 2009-10-30 | 2014-09-17 | 住友化学株式会社 | Pest control composition and pest control method |
| JP5652080B2 (en) * | 2009-10-30 | 2015-01-14 | 住友化学株式会社 | Pest control composition and pest control method |
| AU2011250709A1 (en) * | 2010-11-30 | 2012-06-14 | Sumitomo Chemical Company, Limited | Pesticidal composition and method for controlling pests |
| CN103168794B (en) * | 2011-12-26 | 2014-09-10 | 江苏扬农化工股份有限公司 | Meperfluthrin-containing compound insecticidal composition and application thereof |
| CN103168791B (en) * | 2011-12-26 | 2015-04-08 | 江苏扬农化工股份有限公司 | Meperfluthrin-containing compound insecticidal composition and application thereof |
| CN103168793B (en) * | 2011-12-26 | 2015-04-08 | 江苏扬农化工股份有限公司 | Meperfluthrin-containing compound insecticidal composition and application thereof |
| CN103168792B (en) * | 2011-12-26 | 2015-04-08 | 江苏扬农化工股份有限公司 | Meperfluthrin-containing compound insecticidal composition and application thereof |
| CN102584592B (en) * | 2011-12-28 | 2014-10-15 | 李进 | Deuterated pyrethroid compound and preparation method and application thereof |
| CN104628570B (en) * | 2013-11-15 | 2017-08-08 | 江苏扬农化工股份有限公司 | A kind of clean method for producing of fluorine chlorine ether chrysanthemum ester |
| CN105685083A (en) * | 2014-11-24 | 2016-06-22 | 江苏扬农化工股份有限公司 | Health insecticidal composition containing meperfluthrin and fipronil |
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| CN102283240A (en) * | 2011-06-29 | 2011-12-21 | 贵阳柏丝特化工有限公司 | Pesticide composition |
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| MY178016A (en) | 2020-09-29 |
| WO2009132526A1 (en) | 2009-11-05 |
| CN101306997A (en) | 2008-11-19 |
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