CN111771883A - High-efficiency insecticidal aerosol and preparation method thereof - Google Patents
High-efficiency insecticidal aerosol and preparation method thereof Download PDFInfo
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- CN111771883A CN111771883A CN201911248282.6A CN201911248282A CN111771883A CN 111771883 A CN111771883 A CN 111771883A CN 201911248282 A CN201911248282 A CN 201911248282A CN 111771883 A CN111771883 A CN 111771883A
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- 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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
- A01N25/06—Aerosols
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- 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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
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- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
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- 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
- A01N65/00—Biocides, pest repellants or attractants, or plant growth regulators containing material from algae, lichens, bryophyta, multi-cellular fungi or plants, or extracts thereof
- A01N65/08—Magnoliopsida [dicotyledons]
- A01N65/12—Asteraceae or Compositae [Aster or Sunflower family], e.g. daisy, pyrethrum, artichoke, lettuce, sunflower, wormwood or tarragon
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
- C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
- C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides a high-efficiency insecticidal aerosol, which comprises a component A: 0.1-0.5% by weight of a 1,2, 4-oxadiazole derivative of the formula I: 1-1.5% by weight of marigold extract, component C: 3-73.9% by weight of a solvent and component D: 25-95% by weight of a propellant;
wherein R is CH3、CH2CH3、CH2CH2CH3、CH2CH2CH2CH3(ii) a The propellant is selected from one of liquefied petroleum gas, propane and butane, dimethyl ether or compressed air. The compound of the formula I has a good insecticidal effect, has a synergistic effect after being compounded with marigold extract, and has a remarkable control effect on houseflies, culex pipiens pallens, diamond back moths, armyworms, aphids, tetranychus cinnabarinus and the like.
Description
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a high-efficiency pesticide aerosol and a preparation method thereof.
Background
The existing pesticide aerosol mostly adopts kerosene as a solvent, has the defects that the kerosene is deposited on the ground and the surface of an object after spraying to leave oily marks, and the kerosene has unpleasant smell because of containing a small amount of aromatic hydrocarbons and sulfides. In order to overcome the above-mentioned disadvantages of kerosene, the use of ethanol as a solvent is an alternative, because ethanol has the advantages of low odor and rapid volatilization. However, as for the aerosol insecticide, the proportion of the alcohol-based aerosol insecticide using ethanol as a solvent in the market is far lower than that of the oil-based aerosol insecticide using kerosene as a solvent, and the main reason is that the alcohol-based aerosol insecticide has a significantly lower pest killing effect than the oil-based aerosol insecticide using the same insecticide component, because the kerosene solvent helps the insecticide to rapidly penetrate through the body surface of the insect, and ethanol has a higher polarity, is poorly compatible with the hydrophobic surface layer of the insect, has a high volatilization speed, has a short retention time on the body surface of the insect, and is not beneficial to the effect of the aerosol insecticide.
However, none of the prior art disclosed in the prior art can solve the above problems, for example, chinese patent CN 1628518A discloses an alcohol-based aerosol pesticide technology, which uses 0.1-0.8 wt% pyrethrin as pesticide, 35-60 wt% ethanol as solvent, and does not solve the problem of inhibiting pesticide effect by ethanol as solvent. Chinese patent CN 102669092B discloses a homogeneous high-efficiency water-based pesticide aerosol formulation with low VOC content, which adopts 53.5 wt% deionized water and 15 wt% 95% edible alcohol as solvents, and also does not solve the problem of inhibiting pesticide effect of the solvents due to poorer permeability of water to pest surfaces.
Disclosure of Invention
The invention aims to provide an insecticidal aerosol agent with high efficiency and a preparation method thereof.
The inventor synthesizes the 1,2, 4-diazole derivative as an insecticide and simultaneously unexpectedly finds that the 1,2, 4-diazole derivative has remarkable control effects on houseflies, culex pipiens pallens, diamond back moths, armyworms, aphids, tetranychus cinnabarinus and the like when being mixed with marigold extracts.
The technical scheme of the invention is realized as follows:
the invention provides a high-efficiency insecticidal aerosol, which comprises a component A: 0.1-0.5% by weight of a 1,2, 4-oxadiazole derivative of the formula I: 1-1.5% by weight of marigold extract, component C: 3-73.9% by weight of a solvent and component D: 25-95% by weight of a propellant;
wherein R is CH3、CH2CH3、CH2CH2CH3、CH2CH2CH2CH3；
The propellant is selected from one of liquefied petroleum gas, propane and butane, dimethyl ether or compressed air.
As a further improvement of the invention, the solvent of the component C is one or a mixture of more of alkane solvents of C10-18, water or small molecule alcohol solvents of C2-C8.
As a further improvement of the invention, the marigold extract is prepared by the following method:
s1, raw material preparation: cleaning flos Tagetis Erectae, drying, and pulverizing to obtain flos Tagetis Erectae powder;
s2, ultrasonic-assisted water extraction: adding flos Tagetis Erectae powder into water, stirring, heating to 35-50 deg.C, ultrasonic extracting for 0.5-1 hr, filtering, and retaining residue;
s3, supercritical fluid extraction: extracting the filter residue obtained in the step S2 by using supercritical fluid to obtain extract liquor;
s4, preparing a cinnamon extract: combining the extracts obtained in step S2 and step S3, and mixing well to obtain marigold extract.
As a further improvement of the invention, the mass-volume ratio of the marigold powder to water is 1: (5-10) g/mL; the aerosol as claimed in claim 3, wherein the ultrasonic power is 1000- > 1200W; what is needed isThe supercritical fluid extraction conditions are as follows: extraction pressure: 22-27 MPa; the extraction temperature is as follows: 35-40 ℃; CO 22Flow rate: 7-12L/h; extraction time: 1-2 h; entrainer: glycerin and water in a volume ratio of 1: 1.
As a further improvement of the invention, the 1,2, 4-diazole derivative shown in the formula I is prepared by the following method:
s1, synthesis of an intermediate A: mixing hydroxylamine hydrochloride, propanol and triethylamine, heating to 50 ℃ under the stirring condition, adding benzonitrile, heating a reaction system to reflux, reacting for 1-2h, distilling the reaction system under reduced pressure after the reaction is completed to remove most of propanol, adding water, filtering and drying to obtain an intermediate A, wherein the intermediate A has a structure shown in a following formula II;
s2, synthesizing an intermediate B: slowly dropwise adding substituted acyl chloride into the reaction system under the condition of stirring in an ice water bath to replace acyl chloride, continuously reacting for 2-3h after dropwise adding is finished until the intermediate A completely reacts, adding ethyl acetate into the reaction system for extraction and liquid separation, drying the upper layer of ethyl acetate by using anhydrous sodium sulfate, removing ethyl acetate through reduced pressure distillation, recrystallizing by using ethanol, filtering and drying to obtain an intermediate B, wherein the intermediate B has a structure shown in a following formula III;
s3: synthesis of intermediate C: mixing the intermediate B and dichloromethane, heating under stirring for reflux reaction for 2-4h until the compound B completely reacts, and performing reduced pressure suspension evaporation to remove dichloromethane to obtain oily liquid serving as an intermediate C, wherein the intermediate C has a structure shown in a following formula IV;
s4, synthesizing the 1,2, 4-diazole derivative shown in the formula I: adding the intermediate C, heptafluoro isopropyl iodide, hexadecyl trimethyl ammonium bromide and sodium persulfate into a solvent, wherein the solvent is obtained by mixing methyl tert-butyl ether and water according to the volume ratio of 1:1, reacting for 2-3h under the stirring condition until the compound C completely reacts, adding ethyl acetate for extraction and liquid separation, drying the upper layer of ethyl acetate with anhydrous sodium sulfate, and removing the ethyl acetate through reduced pressure distillation to obtain oily liquid, namely the 1,2, 4-diazole derivative shown in the formula I.
As a further improvement of the present invention, the ratio of the amounts of the hydroxylamine hydrochloride, benzonitrile and triethylamine in step S1 is (1-1.2): 1: (1-1.2); the mass-volume ratio of the cyanophenyl to the propanol is 1 (20-40) g/mL.
As a further improvement of the present invention, the ratio of the amounts of the intermediate a, the substituted acid chloride and the triethylamine in step S2 is 1: (1-1.2): (1-1.2); the mass-volume ratio of the intermediate A to acetone is 1: (15-20) g/mL.
As a further improvement of the invention, the mass-to-volume ratio of the intermediate B and the dichloromethane in the step S3 is 1 (20-30) g/mL; the ratio of the amounts of the intermediate C, heptafluoroisopropyl iodide, hexadecyltrimethyl ammonium bromide and sodium persulfate in step S4 was 1: (1-1.2): (0.02-0.05): (0.02-0.05); the mass-volume ratio of the intermediate C to the solvent is 1: (10-20) g/mL.
The invention further provides a preparation method of the high-efficiency insecticidal aerosol, which comprises the following steps: dissolving component A in component C at room temperature or 30-60 deg.C, adding component B, homogenizing at 10000r/min for 1-2min to obtain high-efficiency pesticide solution, adding into a can equipped with a valve, and adding D-component propellant into the can under pressure via the valve to obtain a pesticide aerosol.
Specific examples of such solvents include water (boiling point 100 ℃), n-butanol (boiling point 117.9 ℃), sec-butanol (boiling point 99.5 ℃), tert-butanol (boiling point 82.3 ℃), n-propanol (boiling point 97.2 ℃), isopropanol (boiling point 82.4 ℃), ethanol (boiling point 78.3 ℃), hexane (boiling point 69 ℃), heptane (boiling point 98.4 ℃), dimethylpentane (boiling point 60 ℃), 2, 2-dimethylbutane (boiling point 50 ℃), octane (boiling point 125 ℃), nonane (boiling point 149.5 ℃), decane (boiling point 174 ℃), undecane (boiling point 195.9 ℃), dodecane (boiling point 216 ℃), tridecane (boiling point 235.4 ℃), tetradecane (boiling point 253.7 ℃), D30 (Exchenmeifu petrochemical company, boiling point 141 ℃ -159 ℃), D40 (Exchenmeifu petrochemical company, boiling point 168 ℃ -60) (Exchen Mobil petrochemical company, boiling point 186 ℃ to 201 ℃, D80 (Exxon Mobil petrochemical, boiling point 206 ℃ to 243 ℃), D110 (Exxon Mobil petrochemical, boiling point 249 ℃ to 267 ℃), Isopar-E (Exxon Mobil petrochemical, boiling point 115 ℃ to 140 ℃), Isopar-G (Exxon Mobil petrochemical, boiling point 167 ℃ to 176 ℃), Isopar-H (Exxon Mobil petrochemical, boiling point 179 ℃ to 188 ℃), Isopar-L (Exxon Mobil petrochemical), boiling point 186 ℃ to 201 Isopar-M (Exxon Mobil petrochemical, boiling point 223 ℃ to 253 ℃), and the like. An alcohol may also be added as a solvent to the intimate mixture providing the water-based aerosol formulation.
An insecticidal aerosol can is prepared by mixing the above components A, B and C, optionally with synergist, fragrance, bactericide, phenol-type stabilizer such as BHT and BHA, etc., at room temperature or heated to 30-60 deg.C, adding into a can equipped with a valve, and adding D propellant selected from liquefied petroleum gas, propane and butane, dimethyl ether or compressed air, preferably propane and butane, into the can under pressure through the valve.
The invention further protects the application of the high-efficiency insecticidal aerosol in the aspect of preventing and controlling sanitary pests such as mosquitoes, flies, moths, armyworms, aphids and mites.
The invention has the following beneficial effects: experiments prove that the compound shown in the formula I has a good insecticidal effect, has a synergistic effect after being compounded with marigold extract, and has a remarkable control effect on houseflies, culex pipiens pallens, diamond back moths, armyworms, aphids, tetranychus cinnabarinus and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1 high-efficiency insecticidal Aerosol
And (2) component A: 0.1% by weight of a 1,2, 4-oxadiazole derivative of formula I;
and (B) component: 1% by weight of marigold extract;
and (3) component C: 3% by weight of a C10-18 alkane solvent;
and (3) component D: 95% by weight of liquefied petroleum gas.
The marigold extract is prepared by the following method:
s1, raw material preparation: cleaning flos Tagetis Erectae, drying, and pulverizing to obtain flos Tagetis Erectae powder;
s2, ultrasonic-assisted water extraction: adding 10g of marigold powder into 50mL of water, stirring uniformly, heating to 35 ℃, performing ultrasonic wave (power is 1000W) assisted extraction for 0.5h, filtering, and reserving filter residues for use;
s3, supercritical fluid extraction: and (4) performing supercritical fluid extraction on the filter residue obtained in the step (S2) to obtain an extract, wherein the supercritical fluid extraction conditions are as follows: extraction pressure: 22 MPa; the extraction temperature is as follows: 35 ℃; CO 22Flow rate: 7L/h; extraction time: 1 h; entrainer: glycerol and water in a volume ratio of 1: 1;
s4, preparing the marigold extract: combining the extracts obtained in step S2 and step S3, and mixing well to obtain marigold extract.
The 1,2, 4-diazole derivative shown in formula I is prepared by the following method:
the chemical equation is as follows:
s1, synthesis of an intermediate A: mixing 0.1mol of hydroxylamine hydrochloride, 497mL of propanol and 0.1mol of triethylamine, heating to 50 ℃ under the condition of stirring, adding 0.1mol of benzonitrile, heating the reaction system to reflux, reacting for 1h, distilling the reaction system under reduced pressure after the reaction is completed to remove most of propanol, adding water, filtering and drying to obtain an intermediate A (0.095mol, the yield is 95%), wherein the intermediate A has a structure shown in the following formula II;
s2, synthesizing an intermediate B: slowly dropwise adding 0.095mol of propionyl chloride into a reaction system under the condition of stirring in an ice water bath, 190mL of acetone and 0.095mol of triethylamine, continuously reacting for 2h after dropwise adding is finished until the intermediate A completely reacts, adding 100mL of ethyl acetate into the reaction system for extracting and separating liquid, drying the upper layer of ethyl acetate with anhydrous sodium sulfate, distilling under reduced pressure to remove ethyl acetate, recrystallizing with ethanol, filtering and drying to obtain an intermediate B (0.0874mol, yield 92%), wherein the intermediate B has a structure shown in the following formula III;
s3: synthesis of intermediate C: 0.0874mol of intermediate B and 230mL of dichloromethane are mixed, the mixture is heated under the stirring condition and refluxed for reaction for 2 hours until the compound B completely reacts, and after the dichloromethane is removed by reduced pressure suspension evaporation, oily liquid is obtained, namely an intermediate C (0.0865mol, the yield is 99%), wherein the intermediate C has a structure shown in a formula IV;
s4, synthesizing the 1,2, 4-diazole derivative shown in the formula I: 0.0865mol of intermediate C, 0.0865mol of heptafluoro isopropyl iodide, 0.00017mol of hexadecyl trimethyl ammonium bromide and 0.00017mol of sodium persulfate are added into 138mL of solvent, the solvent is obtained by mixing methyl tert-butyl ether and water according to the volume ratio of 1:1, the mixture reacts for 2-3h under the stirring condition until the compound C completely reacts, ethyl acetate is added for extraction and liquid separation, the upper layer of ethyl acetate is dried by anhydrous sodium sulfate, and the ethyl acetate is removed by reduced pressure distillation to obtain oily liquid (0.082mol, the yield of 95%) which is the 1,2, 4-oxadiazole derivative shown in the formula I.
The preparation method comprises the following steps:
dissolving component A in component C at room temperature or 45 deg.C, adding component B, homogenizing at 10000r/min for 1.5min to obtain high-efficiency pesticide solution, adding into a can equipped with a valve, and adding D-component propellant into the can under pressure via the valve to obtain a pesticide aerosol.
Example 2 high efficiency insecticidal Aerosol
And (2) component A: 0.3% by weight of a 1,2, 4-oxadiazole derivative of formula I;
and (B) component: 1.2% by weight of marigold extract;
and (3) component C: 35% by weight of a C10-18 alkane solvent;
and (3) component D: 63.5% by weight of propane and butane.
The marigold extract is prepared by the following method:
s1, raw material preparation: cleaning flos Tagetis Erectae, drying, and pulverizing to obtain flos Tagetis Erectae powder;
s2, ultrasonic-assisted water extraction: adding 10g of marigold powder into 100mL of water, stirring uniformly, heating to 50 ℃, performing ultrasonic wave (power is 1200W) assisted extraction for 1h, filtering, and reserving filter residues for use;
s3, supercritical fluid extraction: and (4) performing supercritical fluid extraction on the filter residue obtained in the step (S2) to obtain an extract, wherein the supercritical fluid extraction conditions are as follows: extraction pressure: 27 MPa; the extraction temperature is as follows: 40 ℃; CO 22Flow rate: 12L/h; extraction time: 2 h; entrainer: glycerol and water in a volume ratio of 1: 1;
s4, preparing the marigold extract: combining the extracts obtained in step S2 and step S3, and mixing well to obtain marigold extract.
The 1,2, 4-diazole derivative shown in formula I is prepared by the following method:
the chemical equation is as follows:
s1, synthesis of an intermediate A: mixing 0.11mol of hydroxylamine hydrochloride, 600mL of propanol and 0.11mol of triethylamine, heating to 50 ℃ under the stirring condition, adding 0.1mol of benzonitrile, heating the reaction system to reflux, reacting for 1.5h, distilling the reaction system under reduced pressure after the reaction is completed to remove most of propanol, adding water, filtering and drying to obtain an intermediate A (0.096mol, the yield is 96%), wherein the intermediate A has a structure shown in the following formula II;
s2, synthesizing an intermediate B: slowly dropwise adding 0.11mol of butyryl chloride into a reaction system under the condition of stirring in an ice-water bath, continuously reacting for 2.5h after dropwise adding is finished until the intermediate A completely reacts, adding 100mL of ethyl acetate into the reaction system for extraction and liquid separation, drying the upper layer of ethyl acetate with anhydrous sodium sulfate, distilling under reduced pressure to remove the ethyl acetate, recrystallizing with ethanol, filtering and drying to obtain an intermediate B (0.090mol, yield 94%) which has a structure shown in the following formula III;
s3: synthesis of intermediate C: mixing 0.090mol of intermediate B and 270mL of dichloromethane, heating under stirring and refluxing for reaction for 3h until the compound B completely reacts, and performing reduced pressure suspension distillation to remove dichloromethane to obtain an oily liquid which is intermediate C (0.089mol, yield 99%) having a structure shown in formula IV below;
s4, synthesizing the 1,2, 4-diazole derivative shown in the formula I: adding 0.089mol of intermediate C, 0.098mol of heptafluoro isopropyl iodide, 0.00036mol of hexadecyl trimethyl ammonium bromide and 0.00036mol of sodium persulfate into 200mL of solvent, wherein the solvent is obtained by mixing methyl tert-butyl ether and water according to the volume ratio of 1:1, reacting for 2.5h under the stirring condition until the compound C completely reacts, adding ethyl acetate for extraction and liquid separation, drying the upper layer of ethyl acetate with anhydrous sodium sulfate, and distilling under reduced pressure to remove the ethyl acetate to obtain oily liquid (0.085mol, the yield of 95%) which is the 1,2, 4-oxadiazole derivative shown in the formula I.
The preparation method comprises the following steps:
dissolving component A in component C at room temperature or heated to 30 deg.C, adding component B, homogenizing at 10000r/min for 1min to obtain high-efficiency pesticide solution, adding into a can equipped with a valve, and adding D-component propellant into the can under pressure via the valve to obtain a pesticide aerosol.
Example 3 high-efficiency insecticidal Aerosol
And (2) component A: 0.5% by weight of a 1,2, 4-oxadiazole derivative of formula I;
and (B) component: 1.5% by weight of marigold extract;
and (3) component C: 73.9 percent of small molecular alcohol solvent of C2-C8;
and (3) component D: 25% by weight of dimethyl ether.
The marigold extract is prepared by the following method:
s1, raw material preparation: cleaning flos Tagetis Erectae, drying, and pulverizing to obtain flos Tagetis Erectae powder;
s2, ultrasonic-assisted water extraction: adding 10g of marigold powder into 70mL of water, stirring uniformly, heating to 42 ℃, performing ultrasonic wave (power is 1100W) assisted extraction for 0.75h, filtering, and reserving filter residues for use;
s3, supercritical fluid extraction: and (4) performing supercritical fluid extraction on the filter residue obtained in the step (S2) to obtain an extract, wherein the supercritical fluid extraction conditions are as follows: extraction pressure: 25 MPa; extract (Cuiyu)Taking the temperature: 37 ℃; CO 22Flow rate: 10L/h; extraction time: 1-2 h; entrainer: glycerol and water in a volume ratio of 1: 1;
s4, preparing the marigold extract: combining the extracts obtained in step S2 and step S3, and mixing well to obtain marigold extract.
The 1,2, 4-diazole derivative shown in formula I is prepared by the following method:
the chemical equation is as follows:
s1, synthesis of an intermediate A: mixing 0.12mol of hydroxylamine hydrochloride, 988mL of propanol and 0.12mol of triethylamine, heating to 50 ℃ under the stirring condition, adding 0.1mol of benzonitrile, heating the reaction system to reflux, reacting for 2 hours, distilling the reaction system under reduced pressure after the reaction is completed to remove most of propanol, adding water, filtering and drying to obtain an intermediate A (0.095mol, the yield is 95%), wherein the intermediate A has a structure shown in the following formula II;
s2, synthesizing an intermediate B: slowly dropwise adding 0.114mol of propionyl chloride into a reaction system under the condition of stirring in an ice water bath, continuing to react for 3h after dropwise adding is finished, adding 100mL of ethyl acetate into the reaction system for extraction and liquid separation until the intermediate A completely reacts, drying the upper layer of ethyl acetate with anhydrous sodium sulfate, distilling under reduced pressure to remove the ethyl acetate, recrystallizing with ethanol, filtering and drying to obtain an intermediate B (0.0874mol, yield 92%), wherein the intermediate B has a structure shown in the following formula III;
s3: synthesis of intermediate C: 0.0874mol of intermediate B and 308mL of dichloromethane are mixed, the mixture is heated under the stirring condition and refluxed for reaction for 4 hours until the compound B completely reacts, and after the dichloromethane is removed by reduced pressure suspension evaporation, oily liquid is obtained, namely an intermediate C (0.0865mol, the yield is 99%), wherein the intermediate C has a structure shown in a formula IV;
s4, synthesizing the 1,2, 4-diazole derivative shown in the formula I: 0.0865mol of intermediate C, 0.104mol of heptafluoro isopropyl iodide, 0.00043mol of hexadecyl trimethyl ammonium bromide and 0.00043mol of sodium persulfate are added into 277mL of solvent, the solvent is obtained by mixing methyl tert-butyl ether and water according to the volume ratio of 1:1, the mixture reacts for 3h under the stirring condition until the compound C completely reacts, ethyl acetate is added for extraction and liquid separation, the upper layer of ethyl acetate is dried by anhydrous sodium sulfate, and the ethyl acetate is removed by reduced pressure distillation to obtain oily liquid (0.080mol, yield 92%) which is the 1,2, 4-oxadiazole derivative shown in the formula I.
The preparation method comprises the following steps:
dissolving component A in component C at room temperature or 60 deg.C, adding component B, homogenizing at 10000r/min for 2min to obtain high-efficiency pesticide solution, adding into a can equipped with a valve, and adding D-component propellant into the can under pressure via the valve to obtain a pesticide aerosol.
Test example 1
The preparation examples 1 to 3 of the invention and the commercial insecticide were subjected to indoor efficacy tests on mosquitoes, flies, moths, armyworms, aphids and mites according to GB 13917.2-92. The test insects are culex pipiens with light color, and the female mosquitoes which do not take blood after 2-3 days of emergence; housefly, adult on the fourth day after eclosion; the eclosion of the diamondback moth, adult insects of 2 weeks old, female and male half respectively; sticking the imagoes, wherein the imagoes are half as female and half as male after 2 weeks of eclosion; aphids, adults of 2 weeks after emergence, male and female halves; tetranychus cinnabarinus, adults of 2 weeks after eclosion, female and male half respectively. A closed drum device is adopted. The specific process is as follows: the insect test method comprises the steps of putting tested insects into a cylinder, after the tested insects recover normal activities, quantitatively spraying 1g of medicament from an insecticidal aerosol tank, drawing out a baffle after 1min to enable the tested insects to be in contact with the medicament, immediately timing, starting recording, recording the number of the knocked down tested insects at regular intervals, transferring all tested insects into a clean insect cage after 20min, and checking the number of dead tested insects after 24 h. The results are shown in Table 1 below.
Compared with the prior art, experiments prove that the compound shown in the formula I has a better insecticidal effect, has a synergistic effect after being compounded with marigold extract, and has a remarkable control effect on houseflies, culex pipiens pallens, diamond back moths, armyworms, aphids, tetranychus cinnabarinus and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A highly effective insecticidal aerosol, wherein the aerosol comprises component a: 0.1-0.5% by weight of a 1,2, 4-oxadiazole derivative of the formula I: 1-1.5% by weight of marigold extract, component C: 3-73.9% by weight of a solvent and component D: 25-95% by weight of a propellant;
wherein R is CH3、CH2CH3、CH2CH2CH3、CH2CH2CH2CH3；
The propellant is selected from one of liquefied petroleum gas, propane and butane, dimethyl ether or compressed air.
2. The high-efficiency insecticidal aerosol as claimed in claim 1, wherein the solvent of component C is one or more of alkane solvents of C10-18, water or small molecule alcohol solvents of C2-C8.
3. The aerosol as claimed in claim 1, wherein the marigold extract is prepared by the following steps:
s1, raw material preparation: cleaning flos Tagetis Erectae, drying, and pulverizing to obtain flos Tagetis Erectae powder;
s2, ultrasonic-assisted water extraction: adding flos Tagetis Erectae powder into water, stirring, heating to 35-50 deg.C, ultrasonic extracting for 0.5-1 hr, filtering, and retaining residue;
s3, supercritical fluid extraction: extracting the filter residue obtained in the step S2 by using supercritical fluid to obtain extract liquor;
s4, preparing a cinnamon extract: combining the extracts obtained in step S2 and step S3, and mixing well to obtain marigold extract.
4. The efficient insecticidal aerosol as claimed in claim 3, wherein the mass-volume ratio of marigold powder to water is 1: (5-10) g/mL; the power of the ultrasonic wave is 1000-1200W; the supercritical fluid extraction conditions are as follows: extraction pressure: 22-27 MPa; the extraction temperature is as follows: 35-40 ℃; CO 22Flow rate: 7-12L/h; extraction time: 1-2 h; entrainer: glycerin and water in a volume ratio of 1: 1.
5. The high-efficiency insecticidal aerosol as claimed in claim 1, wherein the 1,2, 4-diazole derivative of formula i is prepared by the following method:
s1, synthesis of an intermediate A: mixing hydroxylamine hydrochloride, propanol and triethylamine, heating to 50 ℃ under the stirring condition, adding benzonitrile, heating a reaction system to reflux, reacting for 1-2h, distilling the reaction system under reduced pressure after the reaction is completed to remove most of propanol, adding water, filtering and drying to obtain an intermediate A, wherein the intermediate A has a structure shown in a following formula II;
s2, synthesizing an intermediate B: slowly dropwise adding substituted acyl chloride into the reaction system under the condition of stirring in an ice water bath to replace acyl chloride, continuously reacting for 2-3h after dropwise adding is finished until the intermediate A completely reacts, adding ethyl acetate into the reaction system for extraction and liquid separation, drying the upper layer of ethyl acetate by using anhydrous sodium sulfate, removing ethyl acetate through reduced pressure distillation, recrystallizing by using ethanol, filtering and drying to obtain an intermediate B, wherein the intermediate B has a structure shown in a following formula III;
s3: synthesis of intermediate C: mixing the intermediate B and dichloromethane, heating under stirring for reflux reaction for 2-4h until the compound B completely reacts, and performing reduced pressure suspension evaporation to remove dichloromethane to obtain oily liquid serving as an intermediate C, wherein the intermediate C has a structure shown in a following formula IV;
s4, synthesizing the 1,2, 4-diazole derivative shown in the formula I: adding the intermediate C, heptafluoro isopropyl iodide, hexadecyl trimethyl ammonium bromide and sodium persulfate into a solvent, wherein the solvent is obtained by mixing methyl tert-butyl ether and water according to the volume ratio of 1:1, reacting for 2-3h under the stirring condition until the compound C completely reacts, adding ethyl acetate for extraction and liquid separation, drying the upper layer of ethyl acetate with anhydrous sodium sulfate, and removing the ethyl acetate through reduced pressure distillation to obtain oily liquid, namely the 1,2, 4-diazole derivative shown in the formula I.
6. The highly effective insecticidal aerosol as claimed in claim 5, wherein the ratio of the amounts of hydroxylamine hydrochloride, benzonitrile and triethylamine in step S1 is (1-1.2): 1: (1-1.2); the mass-volume ratio of the cyanophenyl to the propanol is 1 (20-40) g/mL.
7. The highly effective insecticidal aerosol as claimed in claim 5, wherein the ratio of the amount of the intermediate A, the substituted acyl chloride and the triethylamine in step S2 is 1: (1-1.2): (1-1.2); the mass-volume ratio of the intermediate A to acetone is 1: (15-20) g/mL.
8. The efficient insecticidal aerosol as claimed in claim 5, wherein the mass-to-volume ratio of the intermediate B to the dichloromethane in the step S3 is 1 (20-30) g/mL; the ratio of the amounts of the intermediate C, heptafluoroisopropyl iodide, hexadecyltrimethyl ammonium bromide and sodium persulfate in step S4 was 1: (1-1.2): (0.02-0.05): (0.02-0.05); the mass-volume ratio of the intermediate C to the solvent is 1: (10-20) g/mL.
9. A method for preparing a highly effective insecticidal aerosol as claimed in any one of claims 1 to 8, comprising the steps of: dissolving component A in component C at room temperature or 30-60 deg.C, adding component B, homogenizing at 10000r/min for 1-2min to obtain high-efficiency pesticide solution, adding into a can equipped with a valve, and adding D-component propellant into the can under pressure via the valve to obtain a pesticide aerosol.
10. Use of a highly potent insecticidal aerosol as claimed in any of claims 1 to 8 for controlling mosquitoes, flies, moths, armyworms, aphids and mite pests.
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