CN114698642A - Fragrant insecticide and preparation method thereof - Google Patents

Fragrant insecticide and preparation method thereof Download PDF

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Publication number
CN114698642A
CN114698642A CN202210511597.0A CN202210511597A CN114698642A CN 114698642 A CN114698642 A CN 114698642A CN 202210511597 A CN202210511597 A CN 202210511597A CN 114698642 A CN114698642 A CN 114698642A
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aqueous solution
flavor
synergist
insecticide
fen
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李先明
朱丽娜
李轩祎
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Anhui Langyi Baicao Bioengineering Co ltd
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Anhui Langyi Baicao Bioengineering Co ltd
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Priority to CN202210511597.0A priority Critical patent/CN114698642A/en
Publication of CN114698642A publication Critical patent/CN114698642A/en
Priority to CN202211121305.9A priority patent/CN115251078A/en
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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
    • A01N49/00—Biocides, pest repellants or attractants, or plant growth regulators, containing compounds containing the group, wherein m+n>=1, both X together may also mean —Y— or a direct carbon-to-carbon bond, and the carbon atoms marked with an asterisk are not part of any ring system other than that which may be formed by the atoms X, the carbon atoms in square brackets being part of any acyclic or cyclic structure, or the group, wherein A means a carbon atom or Y, n>=0, and not more than one of these carbon atoms being a member of the same ring system, e.g. juvenile insect hormones or mimics thereof
    • 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
    • A01N27/00—Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/06—Oxygen or sulfur directly attached to a cycloaliphatic ring system
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/14—Ethers
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing aliphatically bound aldehyde or keto groups, or thio analogues thereof; Derivatives thereof, e.g. acetals
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • 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
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
    • 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

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  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Insects & Arthropods (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a fen-flavor insecticide and a preparation method thereof, wherein the fen-flavor insecticide comprises the following components: functional agent, synergist, surfactant, filler and solvent. The functional agent is prepared by mixing geraniol, gingerol, anethole, citral, terpinolene, myrcene, linalyl acetate, furanone, menthol, cinnamaldehyde, citronellal and linalool; the synergist is prepared by reacting 2-aminobenzoic acid with triphosgene to obtain a solid compound, then reacting with methyl iodide in the presence of sodium hydride to obtain a pretreated compound, and then continuously constructing a double-benzene-ring structure through a serial amidation reaction, a decarboxylation reaction and a Pictet-Schpengler reaction. Compared with the prior art, the prepared faint scent type pesticide can attract pests through fragrance, regulate and control the release of calcium ions and hormone level of the pests, reduce the reproductive capacity and generate the effect of killing the pests.

Description

Fragrant insecticide and preparation method thereof
Technical Field
The invention relates to the technical field of pesticides, and particularly relates to a fen-flavor pesticide and a preparation method thereof.
Background
The pests cause serious loss to crops and influence the safe development of human society. For example, cotton bollworm is one of the most destructive agricultural pests, and it can cause damage to many important commercial crops, causing serious economic losses. Currently, pesticides are the fastest available method for controlling pests, especially chemical pesticides. However, abuse of insecticides has not only created resistance problems but also caused a range of environmental and ecological problems, and therefore, the discovery of potential insecticides with novel structures and modes of action has become a hotspot of current insecticide research. The natural product has good environmental compatibility, various biological activities and unique action modes, and can be used as an ideal template compound when searching for more effective novel insecticides. However, natural products also have the disadvantages of long development period, high cost, difficult implementation and poor effect.
The invention patent CN102754660B discloses a preparation method of a sanitary insecticide. Comprises the active ingredient of permethrin, and is added with emulsifier, cosolvent, stabilizer, pH plant essential oil and water. The preparation method of the pesticide of the invention comprises the following steps: firstly, mixing and stirring the chlorenthrin, the emulsifier, the cosolvent and the stabilizer according to the mass fraction to prepare missible oil, then adding the missible oil into water while stirring, and finally adding the plant essential oil and fully stirring until the mixture is clear and transparent. The water-based hygienic insecticide provided by the invention uses water to replace an organic solvent, does not contain a propellant, and is low in preparation cost, convenient to operate and high in production, storage and transportation safety. Compared with the prior art, the water-based sanitary insecticide has better control effect on repelling flies and killing mosquitoes at home. However, the bactericidal composition prepared by the invention has poor drug effect and single insecticidal effect, and can not obviously reduce plant diseases and insect pests.
Disclosure of Invention
In view of the defects of poor pesticide effect and single pesticide effect of natural pesticides in the prior art, the invention aims to provide a fen-flavor pesticide with good pesticide effect and capability of preventing the growth and propagation of diseases and pests.
In order to achieve the purpose of the invention, the invention adopts the following technical scheme:
a faint scent type insecticide comprises the following components: functional agent, synergist, surfactant, filler and solvent.
Preferably, the fen-flavor pesticide comprises the following components in percentage by weight: 30-45% of a functional agent, 10-30% of a synergist, 1-5% of a surfactant, 5-10% of a filler and 30-50% of a solvent.
The fragrant component in the functional agent has a certain attraction effect on pests, and the active bactericidal component can also block the growth of the pests.
The functional agent comprises the following components in percentage by mass: 20-30% of geraniol, 5-10% of gingerol, 10-15% of anethole, 15-20% of citral, 5-10% of terpinolene, 15-25% of myrcene, 1-5% of linalyl acetate, 5-10% of furanone, 0.1-1% of menthol, 1-5% of cinnamaldehyde, 1-3% of citronellal and 1-5% of linalool.
The surfactant is one or a mixture of more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium carboxymethyl cellulose, calcium lignosulfonate, nonylphenol polyoxyethylene aldehyde and styryl phenol polyoxyethylene ether.
The filler is one or a mixture of more of diatomite, bentonite, attapulgite, starch and chitosan.
The solvent is one or a mixture of more of ethylene glycol, polyethylene glycol, propylene glycol and glycerol.
The faint scent type insecticide is prepared by the following method: weighing the component materials according to the formula, dissolving the functional agent and the synergist in the solvent, uniformly stirring, adding the surfactant and the filler, and fully stirring to obtain homogeneous liquid, thus obtaining the fen-flavor pesticide.
The preparation steps of the synergist are as follows:
s1, adding an anhydrous tetrahydrofuran and triphosgene aqueous solution into a 2-aminobenzoic acid aqueous solution, stirring at room temperature, then pouring into ice water, and filtering to obtain a solid compound;
s2, dissolving the solid compound prepared in the step S1 in anhydrous N, N-dimethylformamide, adding an aqueous solution of sodium hydride, stirring for reaction, then dropwise adding an aqueous solution of methyl iodide, after the reaction, pouring the reaction mixture into ice water, and filtering and collecting solids to obtain a pretreated compound;
s3, mixing 5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride aqueous solution, triethyl orthoformate, dimethylacetamide aqueous solution and the pretreated compound prepared in step S2 and adding to high pressure condition, then adding trifluoroacetic acid aqueous solution and triethylenediamine aqueous solution, stirring to react, then pouring into ice water, extracting the solution with ethyl acetate, washing with saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, then evaporating the solvent, purifying the crude product with ethyl acetate/petroleum ether column chromatography to obtain the synergist.
Preferably, the preparation steps of the synergist are as follows, and the parts are all parts by weight:
s1, adding 1-3 parts of anhydrous tetrahydrofuran and 0.2-1 part of 1.0-2 mmol/L triphosgene aqueous solution into 1-5 parts of 3-8 mmol/L2-aminobenzoic acid aqueous solution, stirring at room temperature for 4-8 h, then pouring into 5-15 parts of ice water, and filtering to obtain a solid compound;
s2, dissolving the solid compound prepared in the step S1 in 3-8 parts of anhydrous N, N-dimethylformamide, adding 0.05-0.2 part of 2-6 mmol/L sodium hydride aqueous solution at 0-4 ℃, stirring the reaction mixture for 20-40 min at 0-4 ℃, dropwise adding 0.3-0.8 part of 3.0-3.5 mmol/L methyl iodide aqueous solution, reacting for 1-3 h, pouring the reaction mixture into 5-15 parts of ice water, filtering and collecting solids to obtain a pretreated compound;
s3, mixing 0.1-0.5 part of 1.5-3.0 mmol/L5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride aqueous solution, 0.2-0.6 part of triethyl orthoformate, 0.1-0.3 part of 1.0-3.0 mmol/L dimethylacetamide aqueous solution and the pretreatment compound prepared in the step S2, adding the mixture into an autoclave at a pressure of 1-5 MPa, then adding 0.2-0.6 part of 1-3 mmol/L trifluoroacetic acid aqueous solution and 0.3-0.5 part of 2-4 mmol/L triethylene diamine aqueous solution, stirring the reaction mixture at 80-110 ℃ for 3-8H, pouring the mixture into 5-15 parts of ice water, extracting the solution with 10-30 parts of ethyl acetate for three times, washing with 20-40 parts of saturated sodium chloride, drying with 8-15 parts of anhydrous sodium sulfate, evaporating the solvent, the crude product was purified by ethyl acetate/petroleum ether column chromatography to give the potentiator.
The method comprises the steps of firstly reacting 2-aminobenzoic acid with triphosgene to obtain a solid compound, then reacting with iodomethane in the presence of sodium hydride to obtain a pretreated compound, and then constructing a continuous double benzene ring structure through a serial amidation reaction, a decarboxylation reaction and a Pictet-Schpengler reaction to obtain the synergist. The continuous double-benzene-ring structure of the synergist has a certain growth inhibition effect on pests, the methoxy substituent in the synergist can improve the activity of killing the pests, triethyl orthoformate exists in a position of 1 and 3 bonds as fluorine atoms connected with a carrier, so that the synergist has strong sterilization inhibition performance, RyRs and IP3Rs are two calcium release channels in central neurons ER of insects, and the synergist can act on the RyRs channels to cause the release of calcium ions stored in the central neurons, so that the growth and the propagation of the pests are limited.
The sex pheromone synthesis of insects is influenced by various factors such as nervous system, hormone polypeptide, protein kinase, calcium ion path and the like, and the synergist prepared by the invention can influence the synthesis of sex pheromone components by influencing the calcium ion level and hormone level of pests, so that the pests have diapause phenomenon and the propagation rate is reduced.
Geraniol (trans-3, 7-dimethyl-2, 6-octadien-1-ol) is present in 250 or more plants such as geranium (Pelargonium graveolens L.) belonging to Pelargonium of Bos of Yak family, Cymbopogon (Rutaceae) of Cymbopogon, Litsea cubeba (fruit of Litsea cubeba (Litsea cubeba) of Litsea of Lauraceae), Cymbopogon citratus of Gramineae, and flowers and palms of roses of Rosa of Rosaceae, and has a rose-like floral aroma. The source of the essential oil is extraction and separation from natural essential oil and semi-synthesis or total synthesis, and the essential oil is widely applied to the fields of medicines, tobaccos, food ingredients and the like.
Gingerol is a main flavor developing substance and a functional component with special spicy taste of ginger, contains 3-methoxy-4-hydroxyphenyl functional groups in the structure, comprises gingerol, shogaol, zingerone and gingerol substances, has the activities of antibiosis, antioxidation, insect expelling, cancer resistance and the like, and is widely applied to the industries of food, medicine, cosmetics, health care products and the like.
The anethole has special smell of anethole and contains acetaldehyde and other substances, and is mainly used in daily chemical industry (such as toothpaste, etc.), food, tobacco flavoring agent, medicine, etc.
The citral is a common monoterpene compound, and the natural citral consists of citral in cis and trans configurations, is volatile at normal temperature, is insoluble in water, and has strong lemon fragrance. Can be used for preparing food spice with citrus fragrance, or other spice such as isopulegol, hydroxycitronellal and ionone, and is also important starting material for synthesizing isophytol and vitamins.
The terpinolene exists in elemi oil, cedar oil and other plants, is costustoot gas, can be used for perfumes, food flavors, biological pesticides, cosmetics, cleaning agents and the like, and the high-purity terpinolene can be applied to the fields of engineering plastics, fine chemicals, medicines and the like.
Myrcene has pleasant sweet balsam smell, is an important chemical raw material and intermediate in the perfume industry, is widely applied to synthesis of various rare perfume products such as citronellal, lyral and ambergris ketone, and is also an important raw material in the pharmaceutical industry such as synthesis of vitamins, insect repellents and anti-tumor active substances.
Linalyl acetate, also known as linalyl acetate, has a delicate fragrance similar to that of lilac, lavender and other essential oils, can be widely used for preparing soap essence, perfume essence, cosmetic essence, food essence and other various essences, and has a very wide application range.
Furanones are found in strawberries, oats, mangoes, litchi, malt, gooseberries, grapes, pineapples, and the like. At present, in the actual production process, pyruvaldehyde and zinc powder are reacted, reduced and coupled to obtain 3, 4-dihydroxy-2, 5-hexanedione, and the furanone is prepared through cyclization.
Menthol has characteristic mint flavor and cool mouthfeel, and is widely used in candies, toothpastes and cosmetics as an aromatizing agent. In addition, menthol can be used as irritant in the field of medicine, has the effects of refreshing and relieving itching, and can be used as wind-dispelling medicine for oral administration, and can be used for treating headache, nose and pharyngitis.
Cinnamaldehyde is an evergreen plant of the Lauraceae family. Cinnamon has been widely used in the fields of food, daily chemical products, spices, essence, medicine, and the like.
Citronellal is a flavor used for edible essence, preparing essence of citrus and cherry, also used for preparing soap, used as a raw material of other flavors, and used for synthesizing menthol.
Linalool, a compound of acyclic monoterpene alcohols. The natural linalool is mainly derived from roots, stems and leaves of linalool, and is also present in volatile oil of plants such as jasmine, lavender and the like. Linalool has a dark green and sweet smell of woody, similar to rosewood, and has the fragrance of lilac, lily of the valley and rose, and the fragrance of costus root and fruit.
Compared with the prior art, the invention has the beneficial effects that:
1) the plant extract is used as a functional agent, the emitted fragrance has the function of attracting pests, and the insecticidal compounds are also contained and matched with each other, so that various different types of pests can be controlled, the insecticidal composition is natural and environment-friendly, and the pollution to the environment can be reduced;
2) the method comprises the steps of obtaining a solid compound through reaction of 2-aminobenzoic acid and triphosgene, reacting the solid compound with methyl iodide in the presence of sodium hydride to obtain a pretreated compound, and performing serial amidation reaction, decarboxylation reaction and Pictet-Pengler reaction with 5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride and triethyl orthoformate to generate a synergist, wherein the synergist can reduce reproductive capacity and generate an effect of killing pests by regulating the release of calcium ions and hormone level of the pests, and the synergist can achieve a synergistic effect after being compounded with a functional agent;
Detailed Description
Example 1
A preparation method of a fen-flavor pesticide comprises the following steps: dissolving 2.5kg of functional agent and 1.5kg of synergist in 6kg of glycol, uniformly stirring, adding 0.3kg of sodium carboxymethylcellulose and 0.8kg of diatomite, and fully stirring to obtain homogeneous liquid, thus obtaining the fen-flavor pesticide.
The preparation steps of the synergist are as follows:
s1, adding 2kg of anhydrous tetrahydrofuran and 0.5kg of 1.8mmol/L triphosgene aqueous solution into 3kg of 5 mmol/L2-aminobenzoic acid aqueous solution, stirring at room temperature for 6 hours, then pouring into 10kg of ice water, and filtering to obtain a solid compound;
s2, dissolving the solid compound prepared in the step S1 in 5kg of anhydrous N, N-dimethylformamide, then adding 0.1kg of 4.0mmol/L sodium hydride aqueous solution at 0 ℃, stirring the reaction mixture for 30min at 0 ℃, then dropwise adding 0.5kg of 3.3mmol/L methyl iodide aqueous solution, reacting for 2h, pouring the reaction mixture into 10kg of ice water, filtering and collecting solids to obtain a pretreated compound;
s3, mixing 0.4kg of 2.0mmol/L aqueous 5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride, 0.4kg of triethyl orthoformate, 0.2kg of 2.0mmol/L aqueous dimethylacetamide and the pretreated compound prepared in the step S2, and adding them into an autoclave, the pressure in the autoclave was 3MPa, then 0.4kg of a 2mmol/L aqueous trifluoroacetic acid solution and 0.35kg of a 3mmol/L aqueous triethylenediamine solution were added, the reaction mixture was stirred at 100 ℃ for 6 hours, then poured into 10kg of ice water, the solution was extracted three times with 20kg of ethyl acetate, and washed with 30kg of saturated sodium chloride brine, dried over 10kg of anhydrous sodium sulfate, the solvent was then evaporated and the crude product was purified by ethyl acetate/petroleum ether column chromatography to give the synergist.
The functional agent is formed by mixing 0.5kg of geraniol, 0.2kg of gingerol, 0.3kg of anethole, 0.4kg of citral, 0.2kg of terpinene, 0.4kg of myrcene, 0.1kg of linalyl acetate, 0.2kg of furanone, 0.02kg of menthol, 0.08kg of cinnamaldehyde, 0.05kg of citronellal and 0.05kg of linalool.
Example 2
A fen-flavor insecticide was prepared substantially as in example 1, with the only difference being: the preparation methods of the synergist are not consistent.
The preparation method of the synergist comprises the following steps:
s1, adding 2kg of anhydrous tetrahydrofuran into 3kg of 5 mmol/L2-aminobenzoic acid aqueous solution, stirring at room temperature for 6 hours, then pouring into 10kg of ice water, and filtering to obtain a solid compound;
s2, dissolving the solid compound prepared in the step S1 in 5kg of anhydrous N, N-dimethylformamide, then adding 0.1kg of 4.0mmol/L sodium hydride aqueous solution at 0 ℃, stirring the reaction mixture for 30min at 0 ℃, then dropwise adding 0.5kg of 3.3mmol/L methyl iodide aqueous solution, reacting for 2h, pouring the reaction mixture into 10kg of ice water, filtering and collecting solids to obtain a pretreated compound;
s3, mixing 0.4kg of 2.0mmol/L aqueous 5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride, 0.4kg of triethyl orthoformate, 0.2kg of 2.0mmol/L aqueous dimethylacetamide and the pretreated compound prepared in the step S2, and adding them into an autoclave, the pressure in the autoclave was 3MPa, then 0.4kg of a 2mmol/L aqueous trifluoroacetic acid solution and 0.35kg of a 3mmol/L aqueous triethylenediamine solution were added, the reaction mixture was stirred at 100 ℃ for 6 hours, then poured into 10kg of ice water, the solution was extracted three times with 20kg of ethyl acetate, and washed with 30kg of saturated sodium chloride brine, dried over 10kg of anhydrous sodium sulfate, the solvent was then evaporated and the crude product was purified by ethyl acetate/petroleum ether column chromatography to give the synergist.
The preparation method of the functional agent is the same as that of the embodiment 1.
Example 3
A fen-flavor insecticide was prepared substantially as in example 1, with the only difference being: the preparation methods of the synergist are not consistent.
The preparation method of the synergist comprises the following steps:
s1, mixing 2kg of anhydrous tetrahydrofuran and 0.5kg of 1.8mmol/L triphosgene aqueous solution, stirring at room temperature for 6 hours, then pouring into 10kg of ice water, and filtering to obtain a solid compound;
s2, dissolving the solid compound prepared in the step S1 in 5kg of anhydrous N, N-dimethylformamide, then adding 0.1kg of 4.0mmol/L sodium hydride aqueous solution at 0 ℃, stirring the reaction mixture for 30min at 0 ℃, then dropwise adding 0.5kg of 3.3mmol/L methyl iodide aqueous solution, reacting for 2h, pouring the reaction mixture into 10kg of ice water, filtering and collecting solids to obtain a pretreated compound;
s3, mixing 0.4kg of 2.0mmol/L aqueous 5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride, 0.4kg of triethyl orthoformate, 0.2kg of 2.0mmol/L aqueous dimethylacetamide and the pretreated compound prepared in the step S2, and adding them into an autoclave, the pressure in the autoclave was 3MPa, then 0.4kg of a 2mmol/L aqueous trifluoroacetic acid solution and 0.35kg of a 3mmol/L aqueous triethylenediamine solution were added, the reaction mixture was stirred at 100 ℃ for 6 hours, then poured into 10kg of ice water, the solution was extracted three times with 20kg of ethyl acetate, and washed with 30kg of saturated sodium chloride brine, dried over 10kg of anhydrous sodium sulfate, the solvent was then evaporated and the crude product was purified by ethyl acetate/petroleum ether column chromatography to give the potentiator.
The preparation method of the functional agent is the same as that of the embodiment 1.
Example 4
A fen-flavor insecticide was prepared substantially as in example 1, with the only difference being: the preparation methods of the synergist are not consistent.
The preparation method of the synergist comprises the following steps:
s1, adding 2kg of anhydrous tetrahydrofuran and 0.5kg of 1.8mmol/L triphosgene aqueous solution into 3kg of 5 mmol/L2-aminobenzoic acid aqueous solution, stirring at room temperature for 6 hours, then pouring into 10kg of ice water, and filtering to obtain a solid compound;
s2, dissolving the solid compound prepared in the step S1 in 5kg of anhydrous N, N-dimethylformamide, then adding 0.1kg of 4.0mmol/L sodium hydride aqueous solution at 0 ℃, stirring the reaction mixture for 30min at 0 ℃, then dropwise adding 0.5kg of 3.3mmol/L methyl iodide aqueous solution, reacting for 2h, pouring the reaction mixture into 10kg of ice water, filtering and collecting solids to obtain a pretreated compound;
s3, 0.4kg of 2.0mmol/L aqueous 5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride, 0.2kg of 2.0mmol/L aqueous dimethylacetamide and the pretreated compound prepared in the step S2 are mixed and added into an autoclave at a pressure of 3MPa, followed by addition of 0.4kg of 2mmol/L aqueous trifluoroacetic acid and 0.35kg of 3mmol/L aqueous triethylenediamine, the reaction mixture is stirred at 100 ℃ for 6 hours, then poured into 10kg of ice water, the solution is extracted three times with 20kg of ethyl acetate, and washed with 30kg of saturated sodium chloride brine, dried over 10kg of anhydrous sodium sulfate, then the solvent is evaporated, and the crude product is purified by ethyl acetate/petroleum ether column chromatography to obtain the synergist.
The preparation method of the functional agent is the same as that of the embodiment 1.
Comparative example 1
A fen-flavor insecticide was prepared substantially as in example 1, with the only difference being: the preparation methods of the synergist are not consistent.
The preparation method of the synergist comprises the following steps:
s1, pouring 2kg of anhydrous tetrahydrofuran into 10kg of ice water, and filtering to obtain a compound;
s2, dissolving the compound prepared in the step S1 in 5kg of anhydrous N, N-dimethylformamide, then adding 0.1kg of 4.0mmol/L sodium hydride aqueous solution at 0 ℃, stirring the reaction mixture for 30min at 0 ℃, then dropwise adding 0.5kg of 3.3mmol/L methyl iodide aqueous solution, reacting for 2h, pouring the reaction mixture into 10kg of ice water, filtering and collecting solids to obtain a pretreated compound;
s3, 0.4kg of 2.0mmol/L aqueous 5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride, 0.2kg of 2.0mmol/L aqueous dimethylacetamide and the pretreated compound prepared in the step S2 are mixed and added into an autoclave at a pressure of 3MPa, followed by addition of 0.4kg of 2mmol/L aqueous trifluoroacetic acid and 0.35kg of 3mmol/L aqueous triethylenediamine, the reaction mixture is stirred at 100 ℃ for 6 hours, then poured into 10kg of ice water, the solution is extracted three times with 20kg of ethyl acetate, and washed with 30kg of saturated sodium chloride brine, dried over 10kg of anhydrous sodium sulfate, then the solvent is evaporated, and the crude product is purified by ethyl acetate/petroleum ether column chromatography to obtain the synergist.
The preparation method of the functional agent is the same as that of the embodiment 1.
Comparative example 2
A fen-flavor insecticide was prepared substantially as in example 1, with the only difference being: no synergist was added.
Comparative example 3
A fen-flavor insecticide was prepared substantially as in example 1, with the only difference being: no functional agent is added.
Test example 1
Pesticide effect test in cotton aphid field
The test plants are conventional non-transgenic cotton. The whole experiment is located in Huanggang Hubei, and the experiment has the advantages of uniform soil texture, mild topography and excellent drainage and irrigation. The experiment is arranged by adopting a random block design, the experimental plot is divided into 8 large groups, each large group is divided into 3 small groups, the total number of the large groups is 24 small groups, the samples of the examples and the comparative examples are added with water to prepare 60g/L pesticide spraying, a control group is arranged, the control group adopts clear water, the experimental plot of each group of the 3 small groups is randomly extracted, and the area of each small group is 64 square meters. The distance between the cotton plants is 0.5 m, and the small groups are separated by plastic films. In sunny days, spraying is carried out at the rate of 36 g/hectare, and investigation is carried out once at 1d and 5d after spraying. The investigation object is cotton aphid. The investigation method is a five-point sampling method, five points are respectively taken from east, south, west and north of each cell, 5 plants are randomly selected from each point, the number of cotton aphids on each plant is investigated and counted, and an average value is taken. The population reduction rate and the prevention and treatment effect are calculated by the following formulas after 5 days of pesticide application in a conventional cotton field management mode:
the oral cavity decline rate (%) is [ (number of oral cavities before application of pesticide in control area-number of oral cavities after application of pesticide in control area) ÷ number of oral cavities before application of pesticide in control area ] × 100%
The control effect (%) is [ (population reduction rate in a control area-population reduction rate in a control area) ÷ (population reduction rate in a 1-control area) ] × 100%
The test results are shown in Table 1
Table 1: test result of pesticide effect of cotton aphid in field
Scheme(s) Before application Application of drugs 1d Applying medicine for 5d Rate of oral cavity decline Controlling effect
Example 1 529 230 103 80.5％ 87.5％
Example 2 527 315 195 63.0％ 76.2％
Example 3 515 301 189 63.3％ 76.4％
Example 4 538 321 204 62.1％ 75.6％
Comparative example 1 550 438 341 38.0％ 60.1％
Comparative example 2 525 424 330 37.1％ 59.6％
Comparative example 3 521 411 302 42.0％ 62.7％
Control group 509 569 792 -55.6％
As can be seen from the test results in table 1, the faint scent insecticide prepared in example 1 has the best field efficacy on aphis gossypii, probably because the present invention first reacts 2-aminobenzoic acid with triphosgene to obtain a solid compound, then reacts with iodomethane in the presence of sodium hydride to obtain a pretreated compound, and then constructs a continuous double benzene ring structure through a cascade amidation reaction, a decarboxylation reaction, and a pick-spengler reaction to obtain a synergist. The double benzene ring structure of the synergist has a certain growth inhibition effect on pests, the methoxyl substituent in the synergist can improve larvicidal activity, triethyl orthoformate is used as fluorine atoms connected with a carrier and exists in the positions of 1 and 3 bonds, the synergist has strong sterilization inhibition performance, calcium ions stored in central neurons can be released, and the growth of pests is limited, and the control effect of the embodiment 1 is better than that of the embodiment 3, probably because the faint scent component in the synergist has a certain attraction effect on cotton aphids, and the active sterilization component can also hinder the growth of the cotton aphids.
Test example 2
Mating test for bollworm
The test subjects were three-day-old, unmated males and females, and the test was divided into 8 groups. Each group contains 30 male moths and 30 female moths. All adults were placed in insect rearing crakers (1.2 mx0.8mx0.8m). The insecticides of the examples and the comparative examples were prepared at 60g/L, cotton leaves were soaked in the insecticide, the control group was soaked with clear water, then the excess liquid was sucked off with filter paper, and 50g of treated cotton leaves were placed in a yarn cage. In a dark room, every 1 hour, 24 times, using a red flashlight (light intensity 0.3lux), and if male moths had mated with female moths, the limes removed the cages from the worm cage and counted. The test results are shown in table 2.
Table 2: mating test results
Test protocol Logarithm of mating
Example 1 5
Example 2 8
Example 3 7
Example 4 9
Comparative example 1 13
Comparative example 2 14
Comparative example 3 13
Control group 23
(the lower the mating number, the greater the inhibitory effect of the insecticide on the mating of cotton bollworms)
From the test results shown in Table 2, the maximum inhibitory effect of the insecticide of example 1 on mating of cotton bollworms may be caused by unstable release of sex pheromone from female moths, and the sex pheromone synthesis of insects is influenced by various factors such as nervous system, hormone-like polypeptide, protein kinase, calcium ion pathway and other factors, and the synergist prepared by the invention can influence the synthesis of sex pheromone components and the calcium ion level of cotton bollworms, so that the cotton bollworms generate diapause phenomenon and the reproduction rate is reduced.
Test example 3
Determination of calcium ion
A culture solution is prepared from 4g/L of glucose, 24g/L of sucrose, 2.5g/L of fructose, 3.3g/L of proline, 13% of fetal calf serum and 1.3% of yeast extract.
8g of sodium chloride, 0.2g of potassium chloride, 1.5g of disodium hydrogen phosphate and 0.25 g of potassium dihydrogen phosphate are dissolved in 950mL of distilled water, the pH is adjusted to 7.2 with 1mol/L hydrochloric acid or 1mol/L aqueous solution of sodium hydroxide, and the solution is dissolved to 1L by adding distilled water. Sterilizing with high pressure steam sterilizing pan at 120 deg.C for 20min to obtain PBS buffer solution, cooling to room temperature, and storing in refrigerator at 4 deg.C.
The autoclaved PBS buffer was pre-cooled in a refrigerator at 4 ℃. Putting bacillus into a centrifuge tube containing 1.5mL of precooled PBS, adding 1mL of 0.2% papain into the centrifuge tube, preserving at 30 ℃ for 10min, then centrifuging at 1000rpm for 4-6 min, sucking away the papain, adding a prepared culture solution, and standing for 5 min. Then, the cells were washed with the culture medium 2 times, the culture medium was carefully aspirated off, 1mL of the culture medium was added again, the mixture was gently blown down with a 100. mu.L pipette tip to obtain a suspension, the suspension was counted under a microscope using a counter, and the concentration of the suspension was adjusted to 3X 106And (2) absorbing 150 mu L of suspension by using a pipette gun, inoculating the suspension into a culture dish, placing the culture dish into a constant-temperature incubator, adding 2-4 mL of culture solution, adding water into the samples of the examples and the comparative examples to prepare 16g/L, dropwise adding 8 mu L of the suspension into the culture dish, culturing at 30 ℃ for 2d, washing for 2 times by using the culture solution, and performing calcium ion test.
The calcium ion test was measured and recorded using an ion proportional imaging system, setting excitation light at 340nm and 380nm, respectively, and emission light at 510 nm. The recording software was metaflow software in metaimagingseries7.5, setting the measurement time interval to 3s, starting to measure and record the Ratio value of 340/380 for the target cells. The Ratio value and the calcium ion concentration have a direct corresponding relation, namely the concentration of the calcium ions can be directly reflected.
Each of the examples and comparative samples was tested in triplicate and averaged. The test results are shown in Table 3.
Table 3: test results for calcium ion
Figure BDA0003638199120000131
Figure BDA0003638199120000141
As can be seen from the test results in Table 3, the lowest Ratio value in example 1 indicates that the loss of calcium ions in Bacillus is the most serious, probably because the invention can cause the release of calcium ions stored in central neurons by synthesizing the synergist, activate calcium channels, release the stored calcium ions from Bacillus to the outside of the body, cause inactivation and enhance the insecticidal effect.

Claims (9)

1. The fen-flavor insecticide is characterized by comprising the following components: functional agent, synergist, surfactant, filler and solvent.
2. The fen-flavor insecticide as claimed in claim 1, comprising the following components in percentage by weight: 30-45% of a functional agent, 10-30% of a synergist, 1-5% of a surfactant, 5-10% of a filler and 30-50% of a solvent.
3. The fen-flavor insecticide as claimed in claim 1 or 2, wherein the functional agent is prepared by mixing the following components in percentage by mass: 20-30% of geraniol, 5-10% of gingerol, 10-15% of anethole, 15-20% of citral, 5-10% of terpinolene, 15-25% of myrcene, 1-5% of linalyl acetate, 5-10% of furanone, 0.1-1% of menthol, 1-5% of cinnamaldehyde, 1-3% of citronellal and 1-5% of linalool.
4. A fen-flavor insecticide as claimed in claim 1 or 2 wherein: the surfactant is one or a mixture of more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, sodium carboxymethyl cellulose, calcium lignosulphonate, nonylphenol polyoxyethylene aldehyde and styryl phenol polyoxyethylene ether.
5. A fen-flavor insecticide as claimed in claim 1 or 2 wherein: the filler is one or a mixture of more of diatomite, bentonite, attapulgite, starch and chitosan.
6. A fen-flavor insecticide as claimed in claim 1 or 2 wherein: the solvent is one or a mixture of more of ethylene glycol, polyethylene glycol, propylene glycol and glycerol.
7. A fen-flavor insecticide as claimed in claim 1 or 2, wherein said synergist is prepared by the steps of:
s1, adding an anhydrous tetrahydrofuran and triphosgene aqueous solution into a 2-aminobenzoic acid aqueous solution, stirring at room temperature, then pouring into ice water, and filtering to obtain a solid compound;
s2, dissolving the solid compound prepared in the step S1 in anhydrous N, N-dimethylformamide, adding an aqueous solution of sodium hydride, stirring for reaction, dropwise adding an aqueous solution of methyl iodide, after the reaction, pouring the reaction mixture into ice water, and filtering and collecting solids to obtain a pretreated compound;
s3, mixing 5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride aqueous solution, triethyl orthoformate, dimethylacetamide aqueous solution and the pretreated compound prepared in step S2 and adding to high pressure condition, then adding trifluoroacetic acid aqueous solution and triethylenediamine aqueous solution, stirring to react, then pouring into ice water, extracting the solution with ethyl acetate, washing with saturated sodium chloride aqueous solution, drying with anhydrous sodium sulfate, then evaporating the solvent, purifying the crude product with ethyl acetate/petroleum ether column chromatography to obtain the synergist.
8. The fen-flavor insecticide as claimed in claim 7, wherein the preparation steps of the synergist are as follows, and the parts are all by weight:
s1, adding 1-3 parts of anhydrous tetrahydrofuran and 0.2-1 part of 1.0-2 mmol/L triphosgene aqueous solution into 1-5 parts of 3-8 mmol/L2-aminobenzoic acid aqueous solution, stirring at room temperature for 4-8 hours, then pouring into 5-15 parts of ice water, and filtering to obtain a solid compound;
s2, dissolving the solid compound prepared in the step S1 in 3-8 parts of anhydrous N, N-dimethylformamide, adding 0.05-0.2 part of 2-6 mmol/L sodium hydride aqueous solution at 0-4 ℃, stirring the reaction mixture for 20-40 min at 0-4 ℃, dropwise adding 0.3-0.8 part of 3.0-3.5 mmol/L methyl iodide aqueous solution, reacting for 1-3 h, pouring the reaction mixture into 5-15 parts of ice water, filtering and collecting solids to obtain a pretreated compound;
s3, mixing 0.1-0.5 part of 1.5-3.0 mmol/L5, 6-diethyl-2, 3-dihydro-1H-indene-2-amine hydrochloride aqueous solution, 0.2-0.6 part of triethyl orthoformate, 0.1-0.3 part of 1.0-3.0 mmol/L dimethylacetamide aqueous solution and the pretreatment compound prepared in the step S2, adding the mixture into an autoclave at a pressure of 1-5 MPa, then adding 0.2-0.6 part of 1-3 mmol/L trifluoroacetic acid aqueous solution and 0.3-0.5 part of 2-4 mmol/L triethylene diamine aqueous solution, stirring the reaction mixture at 80-110 ℃ for 3-8H, then pouring into 5-15 parts of ice water, extracting the solution with 10-30 parts of ethyl acetate for three times, washing with 20-40 parts of saturated sodium chloride, drying with 8-15 parts of anhydrous sodium sulfate, then evaporating the solvent, the crude product was purified by ethyl acetate/petroleum ether column chromatography to give the synergist.
9. The method for preparing fen-flavor insecticide according to claims 1 to 8, comprising the following steps: weighing the component materials according to the formula, dissolving the functional agent and the synergist in the solvent, uniformly stirring, adding the surfactant and the filler, and fully stirring to obtain homogeneous liquid, thus obtaining the fen-flavor pesticide.
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