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CN103232434A - Nicotine compound, preparation method and uses thereof - Google Patents

Nicotine compound, preparation method and uses thereof Download PDF

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Publication number
CN103232434A
CN103232434A CN2013100918288A CN201310091828A CN103232434A CN 103232434 A CN103232434 A CN 103232434A CN 2013100918288 A CN2013100918288 A CN 2013100918288A CN 201310091828 A CN201310091828 A CN 201310091828A CN 103232434 A CN103232434 A CN 103232434A
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solvent
compound
reaction
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follows
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CN103232434B (en
Inventor
唐剑峰
王如军
刘杰
吴雪
牛纪胜
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SHANDONG UNITED PESTICIDE INDUSTRY Co Ltd
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SHANDONG UNITED PESTICIDE INDUSTRY Co Ltd
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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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
    • 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
    • A01N43/74—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 one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing three or more hetero rings

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Plant Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Pyridine Compounds (AREA)

Abstract

The invention provides a nicotine compound, a preparation method and uses thereof. The nicotine compound has a structural general formula represented by a formula I. The present invention discloses the general formula of the nicotine compound, the preparation method of the nicotine compound, and uses of the nicotine compound in pesticide fields, wherein the nicotine compound can be used for killing larva and imago of Lepidoptera, Homoptera, Coleoptera and Orthoptera.

Description

Nicotine compound and preparation method and application thereof
Technical Field
The invention belongs to the field of pesticides, and particularly relates to a nicotine compound and a preparation method and application thereof.
Background
In modern agricultural production, overuse of pesticides is caused to guarantee production of crops, so that various plant diseases and insect pests generate drug resistance. The existing pesticide has greatly reduced pest killing rate. The problem of imidacloprid resistance, the pesticide used in the largest amount at present, is discussed in the section 1 of the report on agricultural science of China, volume 22, and the resistance levels of pests in four areas of Shandong to imidacloprid are measured by a capillary dripping method, and the pests are found to generate different degrees of imidacloprid resistance, wherein the resistance multiple of the Shandong chat population is 9.6 times.
Therefore, the development of a novel pesticide which has high insecticidal activity and is not easy to generate drug resistance is a necessary trend for solving the problem of drug resistance of the existing pesticide to pests.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a nicotine compound, a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that: a nicotinic compound has a general structural formula shown as I:
，
wherein,
R1one selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, and 3,4, 4-trifluoro-3-butenyl;
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
A method of preparing a nicotinic compound comprising the steps of:
dissolving 1mol of phenol in 800ml of N, N-dimethylformamide 500-5 mol of potassium carbonate, stirring for 1-10h at 40-100 ℃, adding 1mol of a compound A, reacting for 1-24h at 50-100 ℃, distilling off the solvent after the reaction is finished, adding water and dichloromethane for extraction, taking a solvent layer, and distilling off the solvent to obtain an intermediate II, wherein the reaction formula is as follows:
Figure 151532DEST_PATH_IMAGE002
；
dissolving 1mol of the intermediate II in 800ml of 50% alcohol-water solution, adding 1-1.05mol of paraformaldehyde and sodium cyanide with the same amount as the paraformaldehyde, reacting at 30-60 ℃ for 1-24h, adding dichloromethane after the reaction is finished, extracting, taking a solvent layer, evaporating the solvent, and carrying out column chromatography separation to obtain an intermediate III, wherein the reaction formula is as follows:
Figure 800819DEST_PATH_IMAGE003
；
dissolving 1mol of compound B in 2000ml of 300-minus-one methanol, adding 1-5mol of thiourea and sodium methoxide with the same amount as the thiourea, carrying out reflux reaction for 8-24h, cooling to room temperature after reaction, adjusting the pH to 5-6 with hydrochloric acid, adding the precipitated crystal into 2000ml of ammonia water with 300-minus-one ammonia water, adding 0.05g of Raney nickel, carrying out reflux reaction for 1-8h, filtering, cooling for crystallization, dissolving the crystal in 1000ml of toluene, adding phosphorus pentachloride with the same amount as the thiourea, carrying out reflux reaction for 1-24h, adjusting the pH to 5-6 with 30% liquid alkali, removing a water layer, and distilling out the solvent to obtain an intermediate IV, wherein the reaction formula is as follows:
Figure 541373DEST_PATH_IMAGE004
；
dissolving 1mol of the intermediate IV and 1mol of the intermediate III in a solvent, adding 1-10mol of alkali, reacting for 1-24h at 25-125 ℃, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain an intermediate V, wherein the reaction formula is as follows:
；
dissolving 1mol of intermediate V and 1mol of compound C in a solvent, adding 1-10mol of alkali, reacting for 1-24h at 25-150 ℃, filtering after the reaction is finished, distilling off the solvent, and separating by column chromatography to obtain the nicotine compound I, wherein the reaction formula is as follows:
；
among them, in compound A, B, C:
R1selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, 3,4, 4-trifluoro-3-butenylOne of (1);
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
The solvent in the fourth step and the fifth step can be one of methanol, ethanol, isopropanol, butanol and N, N-dimethylformamide; the alkali in the fourth step and the fifth step can be one of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium carbonate and sodium carbonate.
A method of preparing a nicotinic compound comprising the steps of:
dissolving 1mol of phenol in 800ml of N, N-dimethylformamide 500-5, adding 1-2mol of potassium carbonate, stirring at 60-80 ℃ for 3-5h, then adding 1mol of compound A, reacting at 60-80 ℃ for 3-4h, evaporating the solvent after the reaction is finished, adding 500ml of water and 500ml of dichloromethane for extraction, taking a solvent layer, and evaporating the solvent to obtain an intermediate II, wherein the reaction formula is as follows:
Figure 264106DEST_PATH_IMAGE007
；
dissolving 1mol of the intermediate II in 800ml of 50% ethanol aqueous solution, adding 1-1.05mol of paraformaldehyde and sodium cyanide with the same amount as the paraformaldehyde, reacting at 45-50 ℃ for 6-10h, adding 500ml of dichloromethane after the reaction is finished, extracting, taking a solvent layer, distilling off the solvent, and carrying out column chromatography separation to obtain an intermediate III, wherein the reaction formula is as follows:
Figure 124746DEST_PATH_IMAGE003
；
dissolving 1mol of compound B in 800ml of 500-fold methanol, adding 1-1.05mol of thiourea and sodium methoxide with the same amount as the thiourea, carrying out reflux reaction for 8-10h, cooling to room temperature after the reaction, adjusting the pH to 5-6 with hydrochloric acid, adding the precipitated crystal into 2000ml of ammonia water with 300-fold ammonia water, adding 0.05g of Raney's nickel, carrying out reflux reaction for 1-8h, filtering, cooling for crystallization, dissolving the crystal in 1000ml of toluene, adding phosphorus pentachloride with the same amount as the thiourea, carrying out reflux reaction for 6-8h, adjusting the pH to 5-6 with 30% liquid alkali, removing a water layer and a solvent, and distilling out to obtain an intermediate IV, wherein the reaction formula is as follows:
Figure 372188DEST_PATH_IMAGE008
；
dissolving 1mol of the intermediate IV and 1mol of the intermediate III in N, N-dimethylformamide, adding 1-2mol of potassium carbonate, reacting for 4-6h at 60-80 ℃, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain an intermediate V, wherein the reaction formula is as follows:
Figure 380595DEST_PATH_IMAGE005
；
dissolving 1mol of intermediate V and 1mol of compound C in N, N-dimethylformamide, adding 1-2mol of potassium carbonate, reacting at 60-80 ℃ for 4-6h, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain a nicotine compound I, wherein the reaction formula is as follows:
Figure 309368DEST_PATH_IMAGE009
；
among them, in compound A, B, C:
R1one selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, and 3,4, 4-trifluoro-3-butenyl;
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
The invention relates to application of a nicotine compound in preparing an insecticide.
The nicotine compound is used for killing larvae and imagoes of Lepidoptera, Homoptera, Coleoptera and Orthoptera.
The nicotine compound can be compounded with other polyesters, nicotine and organic sulfur compounds for use.
The nicotine compound contains a plurality of active groups such as fluorine-containing groups and pyrimidine rings, and has the advantages of high systemic property and good plant permeability when being used as an insecticide, thereby having high insecticidal activity, wide insecticidal spectrum, difficult generation of drug resistance and high environmental compatibility.
According to the preparation method of the nicotine compound, the nicotine compound with the general structural formula I is finally synthesized by gradually synthesizing the intermediates II, III, IV and V, the process flow is simple and easy to operate, the product purity is high, no environmental pollution is caused, and the yield of the final nicotine compound can reach 97 percent.
The nicotine compound has an inhibition effect on the respiratory metabolism of pests, can inhibit the respiration of mitochondria electron transfer between cytochrome b and c1, is an action body of an acetylcholinesterase receptor, interferes the motor nervous system of the pests, and has a killing and preventing effect on target organisms in a contact killing mode, and the killing rate can reach up to 100%.
The nicotine compound has no cross resistance to the existing pesticides of lepidoptera, homoptera, coleopteran and orthoptera pests, and also has better killing activity to pests with drug resistance. The pesticide prepared by using the nicotine compound as an active ingredient is particularly important for guaranteeing agricultural safety production, improving grain yield, preventing and treating plant diseases and insect pests and reducing environmental pollution caused by pesticides.
Detailed Description
The nicotine compound has a structural general formula shown as I:
Figure 86831DEST_PATH_IMAGE001
，
wherein,
R1one selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, and 3,4, 4-trifluoro-3-butenyl;
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
The invention discloses a nicotine compound I, which is represented by the following general structural formula:
nicotine compounds Structural formula (I)
（1）
Figure 442857DEST_PATH_IMAGE010
（2）
（3）
Figure 467762DEST_PATH_IMAGE012
（4）
（5）
Figure 626659DEST_PATH_IMAGE014
（6）
Figure 609659DEST_PATH_IMAGE015
（7）
Figure 880234DEST_PATH_IMAGE016
（8）
Figure 55126DEST_PATH_IMAGE017
（9）
（10）
（11）
（12）
Figure 463267DEST_PATH_IMAGE021
（13）
（14）
Figure 289589DEST_PATH_IMAGE023
（15）
Figure 964284DEST_PATH_IMAGE024
（16）
Figure 425352DEST_PATH_IMAGE025
（17）
（18）
Figure 644292DEST_PATH_IMAGE027
（19）
Figure 122678DEST_PATH_IMAGE028
（20）
Figure 703832DEST_PATH_IMAGE029
（21）
Figure 976681DEST_PATH_IMAGE030
（22）
Figure 580969DEST_PATH_IMAGE031
（23）
Figure 597467DEST_PATH_IMAGE032
（24）
Figure 33127DEST_PATH_IMAGE033
（25）
Figure 476878DEST_PATH_IMAGE034
（26）
（27）
Figure 450967DEST_PATH_IMAGE036
（28）
Figure 678817DEST_PATH_IMAGE037
（29）
Figure 559049DEST_PATH_IMAGE038
（30）
Figure 934666DEST_PATH_IMAGE039
（31）
Figure 292967DEST_PATH_IMAGE040
（32）
Figure 703219DEST_PATH_IMAGE041
（33）
（34）
Figure 153017DEST_PATH_IMAGE043
（35）
Figure 128057DEST_PATH_IMAGE044
（36）
The preparation method of the nicotine compound comprises the following steps:
dissolving 1mol of phenol in 800ml of N, N-dimethylformamide 500-5 mol of potassium carbonate, stirring for 1-10h at 40-100 ℃, adding 1mol of a compound A, reacting for 1-24h at 50-100 ℃, distilling off the solvent after the reaction is finished, adding water and dichloromethane for extraction, taking a solvent layer, and distilling off the solvent to obtain an intermediate II, wherein the reaction formula is as follows:
Figure 552534DEST_PATH_IMAGE007
dissolving 1mol of the intermediate II in 800ml of 50% alcohol-water solution, adding 1-1.05mol of paraformaldehyde and sodium cyanide with the same amount as the paraformaldehyde, reacting at 30-60 ℃ for 1-24h, adding dichloromethane after the reaction is finished, extracting, taking a solvent layer, evaporating the solvent, and carrying out column chromatography separation to obtain an intermediate III, wherein the reaction formula is as follows:
Figure 902744DEST_PATH_IMAGE003
；
dissolving 1mol of compound B in 2000ml of 300-minus-one methanol, adding 1-5mol of thiourea and sodium methoxide with the same amount as the thiourea, carrying out reflux reaction for 8-24h, cooling to room temperature after reaction, adjusting the pH to 5-6 with hydrochloric acid, adding the precipitated crystal into 2000ml of ammonia water with 300-minus-one ammonia water, adding 0.05g of Raney nickel, carrying out reflux reaction for 1-8h, filtering, cooling for crystallization, dissolving the crystal in 1000ml of toluene, adding phosphorus pentachloride with the same amount as the thiourea, carrying out reflux reaction for 1-24h, adjusting the pH to 5-6 with 30% liquid alkali, removing a water layer, and distilling out the solvent to obtain an intermediate IV, wherein the reaction formula is as follows:
Figure 602846DEST_PATH_IMAGE008
；
dissolving 1mol of the intermediate IV and 1mol of the intermediate III in a solvent, adding 1-10mol of alkali, reacting for 1-24h at 25-125 ℃, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain an intermediate V, wherein the reaction formula is as follows:
Figure 659795DEST_PATH_IMAGE005
；
dissolving 1mol of intermediate V and 1mol of compound C in a solvent, adding 1-10mol of alkali, reacting for 1-24h at 25-150 ℃, filtering after the reaction is finished, distilling off the solvent, and separating by column chromatography to obtain the nicotine compound I, wherein the reaction formula is as follows:
Figure 52730DEST_PATH_IMAGE046
among them, in compound A, B, C:
R1one selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, and 3,4, 4-trifluoro-3-butenyl;
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
The preferable technical scheme is as follows:
the solvent in the fourth step and the fifth step can be one of methanol, ethanol, isopropanol, butanol and N, N-dimethylformamide; the alkali in the fourth step and the fifth step can be one of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium carbonate and sodium carbonate. The preferred solvent has high solubility to the reactants, which facilitates the reaction. Preferred bases provide a suitable reaction environment while allowing easy removal of by-products after the reaction.
A method of preparing a nicotinic compound comprising the steps of:
dissolving 1mol of phenol in 800ml of N, N-dimethylformamide 500-5, adding 1-2mol of potassium carbonate, stirring at 60-80 ℃ for 3-5h, then adding 1mol of compound A, reacting at 60-80 ℃ for 3-4h, evaporating the solvent after the reaction is finished, adding 500ml of water and 500ml of dichloromethane for extraction, taking a solvent layer, and evaporating the solvent to obtain an intermediate II, wherein the reaction formula is as follows:
Figure 890236DEST_PATH_IMAGE007
；
dissolving 1mol of the intermediate II in 800ml of 50% ethanol aqueous solution, adding 1-1.05mol of paraformaldehyde and sodium cyanide with the same amount as the paraformaldehyde, reacting at 45-50 ℃ for 6-10h, adding 500ml of dichloromethane after the reaction is finished, extracting, taking a solvent layer, distilling off the solvent, and carrying out column chromatography separation to obtain an intermediate III, wherein the reaction formula is as follows:
Figure 394030DEST_PATH_IMAGE003
；
dissolving 1mol of compound B in 800ml of 500-fold methanol, adding 1-1.05mol of thiourea and sodium methoxide with the same amount as the thiourea, carrying out reflux reaction for 8-10h, cooling to room temperature after the reaction, adjusting the pH to 5-6 with hydrochloric acid, adding the precipitated crystal into 2000ml of ammonia water with 300-fold ammonia water, adding 0.05g of Raney's nickel, carrying out reflux reaction for 1-8h, filtering, cooling for crystallization, dissolving the crystal in 1000ml of toluene, adding phosphorus pentachloride with the same amount as the thiourea, carrying out reflux reaction for 6-8h, adjusting the pH to 5-6 with 30% liquid alkali, removing a water layer and a solvent, and distilling out to obtain an intermediate IV, wherein the reaction formula is as follows:
Figure 305485DEST_PATH_IMAGE008
；
dissolving 1mol of the intermediate IV and 1mol of the intermediate III in N, N-dimethylformamide, adding 1-2mol of potassium carbonate, reacting for 4-6h at 60-80 ℃, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain an intermediate V, wherein the reaction formula is as follows:
；
dissolving 1mol of intermediate V and 1mol of compound C in N, N-dimethylformamide, adding 1-2mol of potassium carbonate, reacting at 60-80 ℃ for 4-6h, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain a nicotine compound I, wherein the reaction formula is as follows:
Figure 194124DEST_PATH_IMAGE047
among them, in compound A, B, C:
R1selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, 3One of 4, 4-trifluoro-3-butenyl;
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
The invention relates to application of a nicotine compound in preparing an insecticide. Can be used as an active component to form an insecticide together with an agriculturally acceptable carrier, wherein the weight percentage of the active component of the insecticide is 0.5 to 90 percent. The pesticide can be prepared into dry powder, visible powder, missible oil, microemulsion, paste, granules, solution and suspending agent according to known methods.
The nicotine compound is used for killing larvae and imagoes of Lepidoptera, Homoptera, Coleoptera and Orthoptera.
The nicotine compound can be compounded with other polyesters, nicotine and organic sulfur compounds to achieve a synergistic effect, and the compounding weight ratio is 1:20-20: 1.
According to the nicotine compound and the preparation method thereof, the following specific examples can be provided according to specific compounds in the table:
example 1 preparation of nicotinic compound (1) the procedure was as follows:
firstly, dissolving 1mol of phenol in 500ml of N, N-dimethylformamide, adding 1mol of potassium carbonate, stirring for 10 hours at 40 ℃, then adding 1mol of trifluorobromomethane, reacting for 24 hours at 50 ℃, evaporating the solvent after the reaction is finished, adding 500ml of water and 500ml of dichloromethane for extraction, taking a solvent layer, and evaporating the solvent to obtain 152.28g of an intermediate II;
dissolving 152.28g of intermediate II in 500ml of 50% methanol aqueous solution, adding 1mol of paraformaldehyde and 1mol of sodium cyanide at 30 ℃ for reacting for 24 hours, adding 500ml of dichloromethane for extraction after the reaction is finished, taking a solvent layer, and distilling off the solvent, wherein 6: 4 (volume ratio) ethyl acetate/petroleum ether column chromatography to obtain 190.65g of intermediate III;
dissolving 1mol of ethyl formylacetate in 300ml of methanol, then adding 1mol of thiourea and 1mol of sodium methoxide, carrying out reflux reaction for 8h, cooling to room temperature after reaction, adjusting the pH to 5 with hydrochloric acid, adding the precipitated crystals into 300ml of ammonia water, adding 0.05g of Raney nickel, carrying out reflux reaction for 1h, filtering, cooling for crystallization, dissolving the crystals in 1000ml of toluene, then adding 1mol of phosphorus pentachloride, carrying out reflux reaction for 1h, adjusting the pH to 5 with 30% liquid alkali, separating a water layer, and distilling out the solvent to obtain 149.04g of an intermediate IV;
149.04g of intermediate IV and 190.65g of intermediate III are dissolved in methanol, 1mol of sodium carbonate is added, the reaction is carried out for 24h at 25 ℃, after the reaction is finished, the solvent is filtered and evaporated, and the reaction temperature is 8: 2 (volume ratio) ethyl acetate/petroleum ether column chromatography to give 297.9g of intermediate v;
and (4) dissolving 297.9g of the intermediate V and 1mol of 2-chloro-5-chloromethyl pyridine in methanol, adding 1mol of sodium carbonate, reacting at 25 ℃ for 24 hours, filtering after the reaction is finished, and distilling off the solvent, wherein the weight ratio of the intermediate V to the solvent is 7: 3 (volume ratio) to obtain 405.84g of nicotinic compound (1), the yield is 89%, the data of elemental analysis: c: 52.53%, H: 3.75%, Cl: 15.51%, F: 12.46%, N: 12.25%, O: 3.50 percent.
Example 2 preparation of nicotinic compound (8) the procedure was as follows:
dissolving 1mol of phenol in 500ml of N, N-dimethylformamide, adding 5mol of potassium carbonate, stirring for 1h at 100 ℃, then adding 1mol of 1-trifluorobromoethane, reacting for 1h at 100 ℃, evaporating the solvent after the reaction is finished, adding 500ml of water and 500ml of dichloromethane for extraction, taking a solvent layer, and evaporating the solvent to obtain 170.72g of an intermediate II;
dissolving 170.72g of intermediate II in 800ml of 50% propanol aqueous solution, adding 1.05mol of paraformaldehyde and 1.05mol of sodium cyanide at 60 ℃ for reaction for 1h, adding 500ml of dichloromethane for extraction after the reaction is finished, taking a solvent layer, distilling off the solvent, and reacting the mixture in the solvent layer by the following steps of 6: 4 (volume ratio) ethyl acetate/petroleum ether column chromatography to obtain 210.24g of intermediate III;
dissolving 1mol of ethyl acetoacetate in 2000ml of methanol, then adding 5mol of thiourea and 5mol of sodium methoxide, carrying out reflux reaction for 24 hours, cooling to room temperature after the reaction, adjusting the pH to 6 with hydrochloric acid, adding the precipitated crystals into 2000ml of ammonia water, adding 0.05g of Raney nickel, carrying out reflux reaction for 24 hours, filtering, cooling for crystallization, dissolving the crystals in 1000ml of toluene, then adding 5mol of phosphorus pentachloride, carrying out reflux reaction for 24 hours, adjusting the pH to 6 with 30% liquid alkali, separating a water layer, and distilling out the solvent to obtain 167.2g of an intermediate IV;
167.2g of intermediate IV and 210.24g of intermediate III are dissolved in butanol, 10mol of sodium hydroxide is added, the reaction is carried out for 1h at 125 ℃, after the reaction is finished, the solvent is filtered and evaporated, and the reaction temperature is 8: 2 (volume ratio) to obtain 337.46g of intermediate V;
dissolving 337.46g of intermediate V and 1mol of 2-chloro-5-chloromethylpyridine in butanol, adding 10mol of sodium hydroxide, reacting at 150 ℃ for 1 hour, filtering after the reaction is finished, and distilling off the solvent, 7: 3 (volume ratio) of ethyl acetate/petroleum ether column chromatography gave 450.12g of nicotinic compound (8) in 93% yield, elemental analysis data: c: 54.44%, H: 4.36%, Cl: 14.61%, F: 11.74%, N: 11.54%, O: 3.30 percent.
Example 3 preparation of nicotinic compound (11) the procedure was as follows:
dissolving 1mol of phenol in 500ml of N, N-dimethylformamide, adding 2mol of potassium carbonate, stirring for 5 hours at 80 ℃, then adding 1mol of 2-chloro-5-trifluoromethylpyridine, reacting for 4 hours at 80 ℃, evaporating the solvent after the reaction is finished, adding 500ml of water and 500ml of dichloromethane for extraction, taking a solvent layer, and evaporating the solvent to obtain 236.61g of an intermediate II;
236.61g of the intermediate II is dissolved in 600ml of 50% ethanol water solution, 1.05mol of paraformaldehyde and 1.05mol of sodium cyanide are added at 50 ℃ to react for 10 hours, after the reaction is finished, 500ml of dichloromethane is added to extract, a solvent layer is taken, the solvent is evaporated, and the ratio of 6: 4 (volume ratio) ethyl acetate/petroleum ether column chromatography to obtain 276.36g of intermediate III;
dissolving 1mol of ethyl acetoacetate in 800ml of methanol, adding 1.05mol of thiourea and 1.05mol of sodium methoxide, carrying out reflux reaction for 10h, cooling to room temperature after reaction, adjusting the pH to 6 with hydrochloric acid, adding the precipitated crystals into 700ml of ammonia water, adding 0.05g of Raney nickel, carrying out reflux reaction for 24h, filtering, cooling for crystallization, dissolving the crystals in 1000ml of toluene, adding 1.05mol of phosphorus pentachloride, carrying out reflux reaction for 8h, adjusting the pH to 5 with 30% liquid alkali, removing a water layer, and distilling out the solvent to obtain 170.72g of an intermediate IV;
170.72g of intermediate IV and 276.36g of intermediate III are dissolved in N, N-dimethylformamide, 2mol of potassium carbonate is added, the reaction is carried out at 80 ℃ for 6h, after the reaction is finished, the solvent is filtered and evaporated, and the reaction time is 8: 2 (volume ratio) ethyl acetate/petroleum ether column chromatography to obtain 409.34g of intermediate V;
dissolving 409.34g of intermediate V and 1mol of 2-chloro-5-chloromethylpyridine in N, N-dimethylformamide, adding 2mol of potassium carbonate, reacting at 80 ℃ for 6 hours, filtering after the reaction is finished, and distilling off the solvent, wherein the weight ratio of the intermediate V to the solvent is 7: 3 (volume ratio) of ethyl acetate/petroleum ether column chromatography gave 530.59g of nicotinic compound (11), with a yield of 97%, elemental analysis data: c: 56.94%, H: 4.04%, Cl: 12.93%, F: 10.39%, N: 12.77%, O: 2.92 percent.
Example 4 preparation of nicotinic compound (24) the procedure was as follows:
dissolving 1mol of phenol in 600ml of N, N-dimethylformamide, adding 1.5mol of potassium carbonate, stirring for 4 hours at 70 ℃, then adding 1mol of 1-bromo-4-trifluorobutene, reacting for 3.5 hours at 70 ℃, evaporating the solvent after the reaction is finished, adding 500ml of water and 500ml of dichloromethane for extraction, taking a solvent layer, and evaporating the solvent to obtain 193.92g of an intermediate II;
dissolving 193.92g of intermediate II in 500ml of 50% ethanol water, adding 1.02mol of paraformaldehyde and 1.02mol of sodium cyanide at 48 ℃, reacting for 8 hours, adding 500ml of dichloromethane after the reaction is finished, extracting, taking a solvent layer, distilling off the solvent, and reacting the mixture in the solvent layer, wherein the weight ratio of (6): 4 (volume ratio) ethyl acetate/petroleum ether column chromatography separation to obtain 235.2g of intermediate III;
dissolving 1mol of ethyl formylacetate in 750ml of methanol, then adding 1.02mol of thiourea and 1.02mol of sodium methoxide, carrying out reflux reaction for 9h, cooling to room temperature after reaction, adjusting the pH to 6 with hydrochloric acid, adding the precipitated crystals into 1000ml of ammonia water, adding 0.05g of Raney nickel, carrying out reflux reaction for 4h, filtering, cooling for crystallization, dissolving the crystals in 1000ml of toluene, then adding 1.02mol of phosphorus pentachloride, carrying out reflux reaction for 7h, adjusting the pH to 6 with 30% liquid alkali, removing a water layer, and distilling out the solvent to obtain 155.2g of an intermediate IV;
and fourthly, dissolving 155.2g of intermediate IV and 235.2g of intermediate III in N, N-dimethylformamide, adding 1.05mol of potassium carbonate, reacting for 5 hours at 70 ℃, filtering after the reaction is finished, and evaporating the solvent, wherein 8: 2 (volume ratio) ethyl acetate/petroleum ether column chromatography to obtain 354.31g of intermediate V;
354.31g of intermediate V and 1mol of 2-chloro-5-chloromethylthiazole are dissolved in N, N-dimethylformamide, 1.5mol of potassium carbonate is added, the reaction is carried out for 5h at 70 ℃, after the reaction is finished, the solvent is filtered and evaporated, and the reaction temperature is 7: 3 (volume ratio) of ethyl acetate/petroleum ether column chromatography gave 476.9g of nicotinic compound (24) with a yield of 95%, elemental analysis data: c: 50.11%, H: 3.80%, Cl: 14.09%, F: 11.32%, N: 11.13%, O: 3.18%, S: 6.37 percent.
Example 5 preparation of nicotinic compound (33) the procedure was as follows:
dissolving 1mol of phenol in 500ml of N, N-dimethylformamide, adding 1mol of potassium carbonate, stirring for 3 hours at 60 ℃, then adding 1mol of 1-difluorobromoethane, reacting for 3 hours at 60 ℃, evaporating the solvent after the reaction is finished, adding 500ml of water and 500ml of dichloromethane for extraction, taking a solvent layer, and evaporating the solvent to obtain 156.42g of an intermediate II;
dissolving 156.42g of intermediate II in 800ml of 50% ethanol water solution, adding 1.05mol of paraformaldehyde and 1.05mol of sodium cyanide at 45 ℃ for reacting for 6h, adding 500ml of dichloromethane for extraction after the reaction is finished, taking a solvent layer, distilling off the solvent, and reacting the mixture in the solvent layer, wherein the ratio of (6): 4 (volume ratio) ethyl acetate/petroleum ether column chromatography to obtain 194.97g of intermediate III;
dissolving 1mol of ethyl n-propionylacetate in 500ml of methanol, then adding 1mol of thiourea and 1mol of sodium methoxide, carrying out reflux reaction for 8 hours, cooling to room temperature after reaction, adjusting the pH to 5 with hydrochloric acid, adding the precipitated crystals into 2000ml of ammonia water, adding 0.05g of Raney nickel, carrying out reflux reaction for 24 hours, filtering, cooling for crystallization, dissolving the crystals in 1000ml of toluene, then adding 1mol of phosphorus pentachloride, carrying out reflux reaction for 6 hours, adjusting the pH to 6 with 30% liquid alkali, removing a water layer, and distilling out the solvent to obtain 182.4g of an intermediate IV;
and fourthly, dissolving 182.4g of intermediate IV and 194.97g of intermediate III in isopropanol, adding 1mol of potassium carbonate, reacting for 4 hours at the temperature of 60 ℃, filtering after the reaction is finished, and distilling off the solvent, wherein the weight ratio of the intermediate IV to the intermediate III is 8: 2 (volume ratio) to obtain 340.8g of an intermediate V;
dissolving 340.8g of intermediate V and 1mol of 2-chloro-5-chloromethyl thiazole in butanol, adding 1mol of sodium hydroxide, reacting for 4 hours at 60 ℃, filtering after the reaction is finished, and distilling off the solvent, 7: 3 (volume ratio) of ethyl acetate/petroleum ether column chromatography gave 466.56g of nicotinic compound (33) in 96% yield, elemental analysis data: c: 51.75%, H: 4.55%, Cl: 14.55%, F: 7.80%, N: 11.50%, O: 3.28%, S: 6.58 percent.
Biological examples:
compared with the prior pesticide, the pesticide prepared by taking all the possible compounds of the nicotine compound represented by the general formula I as active ingredients is characterized in that:
example 1 peach fruit borer (lepidoptera) test:
solvent: 7 parts by weight of dimethylformamide;
emulsifier: 1 part by weight of alkylaryl polyglycol ether;
active ingredients: 1 part by weight of compound (1);
mixing the components according to the weight ratio, and diluting to the required concentration. The peach fruit borers are respectively immersed into the medicaments for treatment according to the insect immersion method and the leaf immersion method of the national standard- (indoor bioassay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) (7 days after drug administration)
Compound (1) 30 98%
Beta-cypermethrin 30 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (1) as an active ingredient is obviously higher than that of the high-efficiency cypermethrin.
Example 2 apple leaf roller (Lepidoptera) test
Solvent: 7 parts by weight of dimethyl sulfoxide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (2)
Mixing the components according to the weight ratio, and diluting to the required concentration. The apple leaf roller is respectively immersed into each medicament for treatment according to the insect immersion method and the leaf immersion method of the national standard-the laboratory bioassay test criteria, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (2) 50 100%
Trichlorfon 50 85%
The results in the table show that the control effect of the pesticide prepared by using the compound (2) as an active ingredient is obviously higher than that of trichlorfon.
Example 3 Helicoverpa armigera (Lepidoptera) test
Solvent: 7 parts by weight of dimethyl sulfoxide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (3)
Mixing the components according to the weight ratio, and diluting to the required concentration. The cotton bollworm is respectively immersed into each medicament for treatment according to the insect immersion and leaf immersion method of the national standard-the laboratory bioassay test criteria, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (3) 30 100%
Beta-cypermethrin 30 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (3) as an active ingredient is obviously higher than that of the high-efficiency cypermethrin.
Example 4 Plutella xylostella (Lepidoptera) assay
Solvent: 7 parts by weight of dimethyl sulfoxide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (4)
Mixing the components according to the weight ratio, and diluting to the required concentration. The diamondback moth is respectively soaked in the medicaments for treatment according to the insect soaking and leaf soaking methods of the national standard-indoor bioassay test criterion, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (4) 30 99%
Abamectin and its preparation method 30 89%
The results in the table show that the control effect of the pesticide prepared by using the compound (4) as an active ingredient is obviously higher than that of abamectin.
Example 5 Gekko Swinhonis (Lepidoptera) test
Solvent: 8 parts by weight of dimethyl sulfoxide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (5)
Mixing the components according to the weight ratio, and diluting to the required concentration. According to the national standard-insect soaking and leaf soaking method of the laboratory bioassay test criteria, the black cutworm is respectively soaked in each medicament for treatment, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (5) 30 100%
Chlorpyrifos 30 85%
The results in the table show that the control effect of the pesticide prepared by using the compound (5) as an active ingredient is obviously higher than that of chlorpyrifos.
Example 6 Prodenia litura (Lepidoptera) test
Solvent: 8 parts by weight of dimethyl sulfoxide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (6)
Mixing the components according to the weight ratio, and diluting to the required concentration. The prodenia litura is respectively soaked in each medicament for treatment according to the insect soaking and leaf soaking method of the national standard- (indoor bioassay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (6) 50 100%
Chlorpyrifos 50 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (6) as an active ingredient is obviously higher than that of chlorpyrifos.
Example 7 beet armyworm (Lepidoptera) assay
Solvent: 8 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (7)
Mixing the components according to the weight ratio, and diluting to the required concentration. According to the national standard-insect soaking and leaf soaking method of the laboratory bioassay test criteria, beet armyworm is respectively soaked in each medicament for treatment, and the results are as follows:
medicament Concentration ppm of Control effect (%) (7 days after drug administration)
Compound (7) 30 95%
Abamectin and its preparation method 30 80%
The results in the table show that the control effect of the pesticide prepared by using the compound (7) as an active ingredient is obviously higher than that of abamectin.
Example 8 Chilo suppressalis (Lepidoptera) assay
Solvent: 8 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (8)
Mixing the components according to the weight ratio, and diluting to the required concentration. The chilo suppressalis is respectively soaked in each medicament for treatment according to the insect soaking and leaf soaking method of the national standard-the laboratory bioassay test criteria, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (8) 30 100%
Cartap for killing snout moth's larva 30 90%
The results in the table show that the prevention and treatment effect of the pesticide prepared by using the compound (8) as an active ingredient is obviously higher than that of cartap.
Example 9 Lepidoptera (Lepidoptera) assay
Solvent: 8 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (9)
Mixing the components according to the weight ratio, and diluting to the required concentration. The pod borers are respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard-the laboratory bioassay test criteria, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (9) 30 100%
Cypermethrin 30 87%
The results in the table show that the control effect of the pesticide prepared by using the compound (9) as an active ingredient is obviously higher than that of cypermethrin.
Example 10 corn borer (Lepidoptera) test
Solvent: 7 parts by weight of dimethyl sulfoxide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (10)
Mixing the components according to the weight ratio, and diluting to the required concentration. The corn borers are respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard-the laboratory bioassay test criteria, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (10) 100 100%
Cypermethrin 100 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (10) as an active ingredient is obviously higher than that of cypermethrin.
Example 11 Pieris rapae (Lepidoptera) test
Solvent: 8 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (11)
Mixing the components according to the weight ratio, and diluting to the required concentration. The pieris rapae are respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard-the laboratory bioassay test criteria, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (11) 60 95%
Azadirachtin extract 60 80%
The results in the table show that the control effect of the insecticide prepared by using the compound (11) as an active ingredient is obviously higher than that of the azadirachtin extract.
Example 12 tea geometrid (Lepidoptera) test
Solvent: 8 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (12)
Mixing the components according to the weight ratio, and diluting to the required concentration. According to the national standard- "indoor biological assay test criteria" insect-soaking and leaf-soaking method, the tea geometrid larva is respectively soaked in each medicament for treatment, and the results are as follows:
medicament Concentration ppm of Control effect (%) (7 days after drug administration)
Compound (12) 100 100%
Deltamethrin 100 80%
The results in the table show that the control effect of the pesticide prepared by using the compound (12) as an active ingredient is obviously higher than that of deltamethrin.
Example 13 trialeurodes vaporariorum (homoptera) test
Solvent: 8 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (13)
Mixing the components according to the weight ratio, and diluting to the required concentration. The trialeurodes vaporariorum is respectively soaked in each medicament for treatment according to the insect soaking and leaf soaking methods of the national standard- (indoor bioassay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) -5 days after application
Compound (13) 50 100%
Imidacloprid 50 70%
The results in the table show that the control effect of the insecticide prepared by using the compound (13) as an active ingredient is obviously higher than that of imidacloprid.
Example 14 Laodelphax striatellus (Homoptera) test
Solvent: 7 parts by weight of dimethyl sulfoxide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (14)
Mixing the components according to the weight ratio, and diluting to the required concentration. The Laodelphax striatellus is respectively soaked in each medicament for treatment according to the insect soaking and leaf soaking method of the national standard- (indoor bioassay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (14) 100 100%
Thiamethoxam 100 85%
The results in the table show that the control effect of the insecticide prepared by using the compound (14) as an active ingredient is obviously higher than that of thiamethoxam.
Example 15 Myzus persicae (Homoptera) test
Solvent: 7 parts by weight of dimethyl sulfoxide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (15)
Mixing the components according to the weight ratio, and diluting to the required concentration. The green peach aphids are respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard- (indoor bioassay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) -5 days after application
Compound (15) 100 100%
Acetamiprid 100 80%
The results in the table show that the control effect of the pesticide prepared by using the compound (15) as an active ingredient is obviously higher than that of acetamiprid.
Example 16 Green plant bug (homoptera) assay
Solvent: 7 parts by weight of dimethyl sulfoxide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (16)
Mixing the components according to the weight ratio, and diluting to the required concentration. The green plant bug is respectively immersed into each medicament for treatment according to the insect immersion and leaf immersion method of the national standard-the laboratory bioassay test criteria, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (16) 80 100%
Malathion 80 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (16) as an active ingredient is obviously higher than that of malathion.
Example 17 Cotton leafhopper (homoptera) test
Solvent: 7 parts by weight of dimethyl sulfoxide
Emulsifier: 2 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (17)
Mixing the components according to the weight ratio, and diluting to the required concentration. The cotton leafhoppers are respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard-the laboratory bioassay test standard, and the results are as follows:
medicament Concentration ppm of Control effect (%) -5 days after application
Compound (17) 60 90%
Biphenthrin 60 70%
The results in the table show that the control effect of the pesticide prepared by using the compound (17) as an active ingredient is obviously higher than that of bifenthrin.
Example 18 Myzus avenae (Homoptera) assay
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (18)
Mixing the components according to the weight ratio, and diluting to the required concentration. The wheat pipe aphids are respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard- (indoor biological assay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) -5 days after application
Compound (18) 60 100%
Imidacloprid 60 90%
The results in the table show that the control effect of the insecticide prepared by using the compound (18) as an active ingredient is obviously higher than that of imidacloprid.
Example 19 Lecanicillium dorferi (homoptera) assay
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (19)
Mixing the components according to the weight ratio, and diluting to the required concentration. The pear garden scale is respectively soaked in each medicament for treatment according to the insect soaking and leaf soaking method of the national standard (national standard) -indoor bioassay test standard, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (19) 100 95%
Methidathion 100 80%
The results in the table show that the control effect of the insecticide prepared by using the compound (19) as an active ingredient is obviously higher than that of methidathion.
Example 20 experiment of Lecanicillium nodosum (Homoptera)
Solvent: 9 parts by weight of dimethyl sulfoxide
Active ingredients: 1 part by weight of Compound (20)
Mixing the components according to the weight ratio, and diluting to the required concentration. The pelago virginiana is respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard-indoor bioassay test criterion, and the results are as follows:
medicament Concentration ppm of Control effect (%) -5 days after application
Compound (20) 100 100%
Pyridaben 100 90%
The results in the table show that the control effect of the insecticide prepared by using the compound (20) as an active ingredient is obviously higher than that of pyridaben.
Example 21 Blooming Lecanis (Homoptera) test
Solvent: 9 parts by weight of dimethyl sulfoxide
Active ingredients: 1 part by weight of Compound (21)
Mixing the components according to the weight ratio, and diluting to the required concentration. The Miyajie is respectively soaked in each medicament for treatment according to the insect soaking and leaf soaking method of the national standard- (indoor bioassay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) -5 days after application
Compound (21) 100 100%
Omethoate fruit 100 80%
The results in the table show that the control effect of the pesticide prepared by using the compound (21) as an active ingredient is obviously higher than that of omethoate.
Example 22 aphid test from radish (homoptera)
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (22)
Mixing the components according to the weight ratio, and diluting to the required concentration. The radish aphids are respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard-the laboratory bioassay test criteria, and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (22) 100 100%
Acetamiprid 100 85%
The results in the table show that the control effect of the pesticide prepared by using the compound (22) as an active ingredient is obviously higher than that of acetamiprid.
Example 23 Aphis gossypii (Homoptera) assay
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (23)
Mixing the components according to the weight ratio, and diluting to the required concentration. The cotton aphids are respectively immersed into various medicaments for treatment according to the insect immersion and leaf immersion method of the national standard- (indoor bioassay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (23) 100 100%
Pyridaben 100 90%
The results in the table show that the control effect of the insecticide prepared by using the compound (23) as an active ingredient is obviously higher than that of pyridaben.
Example 24 brown planthopper (homoptera) assay
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (24)
Mixing the components according to the weight ratio, and diluting to the required concentration. The brown planthopper is respectively soaked in each medicament for treatment according to the insect soaking and leaf soaking method of the national standard- (indoor bioassay test criteria), and the results are as follows:
medicament Concentration ppm of Control effect (%) 3 days after application
Compound (23) 100 100%
Imidacloprid 100 90%
The results in the table show that the control effect of the insecticide prepared by using the compound (24) as an active ingredient is obviously higher than that of imidacloprid.
Example 25 spike beetle (Coleoptera) test
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (25)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (25) 50 100%
Fipronil 50 80%
The results in the table show that the control effect of the pesticide prepared by using the compound (25) as an active ingredient is obviously higher than that of fipronil.
Example 26 test of Flammulina velutipes (Coleoptera)
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (26)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (26) 50 95%
Carbosulfan 50 80%
The results in the table show that the control effect of the pesticide prepared by using the compound (26) as an active ingredient is obviously higher than that of carbosulfan.
Example 27 assay of Viburnus viridis (Coleoptera)
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (27)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of 3 days after the administrationMortality (%)
Compound (27) 50 100%
Fenitrothion 50 85%
The results in the table show that the control effect of the pesticide prepared by using the compound (27) as an active ingredient is obviously higher than that of fenitrothion.
Example 28 striped flea beetle (Coleoptera) test
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (28)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (28) 50 100%
Chlorpyrifos 50 80%
The results in the table show that the control effect of the pesticide prepared by using the compound (28) as an active ingredient is obviously higher than that of chlorpyrifos.
Example 29 Monochamus alternatus (Coleoptera) test
Solvent: 8.5 parts of acetone
Emulsifier: 0.5 parts by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (29)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (29) 50 100%
Methylamino avermectin 50 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (29) as an active ingredient is obviously higher than that of emamectin benzoate.
Example 30 Coleoptera test
Solvent: 8 parts of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (30)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (30) 50 100%
Imidacloprid 50 80%
The results in the table show that the control effect of the insecticide prepared by using the compound (30) as an active ingredient is obviously higher than that of imidacloprid.
Example 31 test of anoplophora chinensis (Coleoptera)
Solvent: 8 parts of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (31)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (31) 50 98%
Imidacloprid 50 85%
The results in the table show that the control effect of the insecticide prepared by using the compound (31) as an active ingredient is obviously higher than that of imidacloprid.
Example 32 Citrus Gilledina (Coleoptera) test
Solvent: 8 parts of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (32)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (32) 50 100%
Chlorpyrifos 50 85%
The results in the table show that the control effect of the pesticide prepared by using the compound (32) as an active ingredient is obviously higher than that of chlorpyrifos.
Example 33 test of weevils (Coleoptera)
Solvent: 8 parts of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether
Active ingredients: 1 part by weight of Compound (33)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test was performed according to the oral bioassay method of national Standard- "laboratory bioassay test guidelines", and the results are given in the following table:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (33) 50 90%
Chlorpyrifos 50 75%
The results in the table show that the control effect of the pesticide prepared by using the compound (33) as an active ingredient is obviously higher than that of chlorpyrifos.
Example 34 locusta migratoria (orthoptera) test in east Asia
Solvent: 9 parts of dimethyl sulfoxide
Active ingredients: 1 part by weight of Compound (34)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test is carried out according to the feed mixing poison method of the national standard- (indoor biological assay test criteria), and the results are as follows:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (34) 100 100%
Flubenuron 100 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (34) as an active ingredient is obviously higher than that of flufenoxuron.
Example 35 locust (Orthoptera) test of Oryza sativa
Solvent: 9 parts of dimethyl sulfoxide
Active ingredients: 1 part by weight of Compound (35)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test is carried out according to the feed mixing poison method of the national standard- (indoor biological assay test criteria), and the results are as follows:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (35) 100 100%
Flubenuron 100 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (35) as an active ingredient is obviously higher than that of flufenoxuron.
Example 36 Gryllotalpa (Lepidoptera) test
Solvent: 9 parts of dimethyl sulfoxide
Active ingredients: 1 part by weight of Compound (36)
Mixing the components according to the weight ratio, and diluting to the required concentration. The test is carried out according to the soil mixed drug feeding method of the national standard-the laboratory bioassay test criterion, and the results are as follows:
medicament Concentration ppm of Mortality rate (%) 3 days after drug administration
Compound (36) 100 100%
Chlorpyrifos 100 90%
The results in the table show that the control effect of the pesticide prepared by using the compound (36) as an active ingredient is obviously higher than that of chlorpyrifos.

Claims (7)

1. A nicotinic compound, characterized in that: has a structural general formula as shown in I:
Figure 2013100918288100001DEST_PATH_IMAGE002
，
wherein,
R1selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, 3,4, 4-trifluoro-One of 3-butenyl;
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
2. A method of preparing a nicotinic compound according to claim 1, wherein: the method comprises the following steps:
dissolving 1mol of phenol in 800ml of N, N-dimethylformamide 500-5 mol of potassium carbonate, stirring for 1-10h at 40-100 ℃, adding 1mol of a compound A, reacting for 1-24h at 50-100 ℃, distilling off the solvent after the reaction is finished, adding water and dichloromethane for extraction, taking a solvent layer, and distilling off the solvent to obtain an intermediate II, wherein the reaction formula is as follows:
；
dissolving 1mol of the intermediate II in 800ml of 50% alcohol-water solution, adding 1-1.05mol of paraformaldehyde and sodium cyanide with the same amount as the paraformaldehyde, reacting at 30-60 ℃ for 1-24h, adding dichloromethane after the reaction is finished, extracting, taking a solvent layer, evaporating the solvent, and carrying out column chromatography separation to obtain an intermediate III, wherein the reaction formula is as follows:
；
dissolving 1mol of compound B in 2000ml of 300-minus-one methanol, adding 1-5mol of thiourea and sodium methoxide with the same amount as the thiourea, carrying out reflux reaction for 8-24h, cooling to room temperature after reaction, adjusting the pH to 5-6 with hydrochloric acid, adding the precipitated crystal into 2000ml of ammonia water with 300-minus-one ammonia water, adding 0.05g of Raney nickel, carrying out reflux reaction for 1-8h, filtering, cooling for crystallization, dissolving the crystal in 1000ml of toluene, adding phosphorus pentachloride with the same amount as the thiourea, carrying out reflux reaction for 1-24h, adjusting the pH to 5-6 with 30% liquid alkali, removing a water layer, and distilling out the solvent to obtain an intermediate IV, wherein the reaction formula is as follows:
Figure DEST_PATH_IMAGE008
；
dissolving 1mol of the intermediate IV and 1mol of the intermediate III in a solvent, adding 1-10mol of alkali, reacting for 1-24h at 25-125 ℃, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain an intermediate V, wherein the reaction formula is as follows:
；
dissolving 1mol of intermediate V and 1mol of compound C in a solvent, adding 1-10mol of alkali, reacting for 1-24h at 25-150 ℃, filtering after the reaction is finished, distilling off the solvent, and separating by column chromatography to obtain the nicotine compound I, wherein the reaction formula is as follows:
Figure DEST_PATH_IMAGE012
；
among them, in compound A, B, C:
R1one selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, and 3,4, 4-trifluoro-3-butenyl;
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
3. A method of preparing a nicotinic compound according to claim 2, wherein: the solvent in the fourth step and the fifth step can be one of methanol, ethanol, isopropanol, butanol and N, N-dimethylformamide; the alkali in the fourth step and the fifth step can be one of sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium carbonate and sodium carbonate.
4. A method of preparing a nicotinic compound according to claims 1-3, characterised in that: the method comprises the following steps:
dissolving 1mol of phenol in 800ml of N, N-dimethylformamide 500-5, adding 1-2mol of potassium carbonate, stirring at 60-80 ℃ for 3-5h, then adding 1mol of compound A, reacting at 60-80 ℃ for 3-4h, evaporating the solvent after the reaction is finished, adding 500ml of water and 500ml of dichloromethane for extraction, taking a solvent layer, and evaporating the solvent to obtain an intermediate II, wherein the reaction formula is as follows:
Figure 267543DEST_PATH_IMAGE004
；
dissolving 1mol of the intermediate II in 800ml of 50% ethanol aqueous solution, adding 1-1.05mol of paraformaldehyde and sodium cyanide with the same amount as the paraformaldehyde, reacting at 45-50 ℃ for 6-10h, adding 500ml of dichloromethane after the reaction is finished, extracting, taking a solvent layer, distilling off the solvent, and carrying out column chromatography separation to obtain an intermediate III, wherein the reaction formula is as follows:
Figure 316401DEST_PATH_IMAGE006
；
dissolving 1mol of compound B in 800ml of 500-fold methanol, adding 1-1.05mol of thiourea and sodium methoxide with the same amount as the thiourea, carrying out reflux reaction for 8-10h, cooling to room temperature after the reaction, adjusting the pH to 5-6 with hydrochloric acid, adding the precipitated crystal into 2000ml of ammonia water with 300-fold ammonia water, adding 0.05g of Raney's nickel, carrying out reflux reaction for 1-8h, filtering, cooling for crystallization, dissolving the crystal in 1000ml of toluene, adding phosphorus pentachloride with the same amount as the thiourea, carrying out reflux reaction for 6-8h, adjusting the pH to 5-6 with 30% liquid alkali, removing a water layer and a solvent, and distilling out to obtain an intermediate IV, wherein the reaction formula is as follows:
Figure 389400DEST_PATH_IMAGE008
；
dissolving 1mol of the intermediate IV and 1mol of the intermediate III in N, N-dimethylformamide, adding 1-2mol of potassium carbonate, reacting for 4-6h at 60-80 ℃, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain an intermediate V, wherein the reaction formula is as follows:
Figure 170405DEST_PATH_IMAGE010
；
dissolving 1mol of intermediate V and 1mol of compound C in N, N-dimethylformamide, adding 1-2mol of potassium carbonate, reacting at 60-80 ℃ for 4-6h, filtering after the reaction is finished, evaporating the solvent, and performing column chromatography separation to obtain a nicotine compound I, wherein the reaction formula is as follows:
Figure DEST_PATH_IMAGE014
，
among them, in compound A, B, C:
R1one selected from trifluoromethyl, 2,2, 2-trifluoroethyl, 2, 2-difluoroethyl, 2-yl-3-chloro-5-trifluoromethylpyridine, 2-yl-5-trifluoromethylpyridine, and 3,4, 4-trifluoro-3-butenyl;
R2selected from 2-chloro-5-methylenepyridine or 2-chloro-5-methylenethiazole;
R3one selected from methyl, ethyl and n-propyl.
5. Use of a nicotinic compound as claimed in claim 1 in the preparation of a pesticide.
6. A nicotinic compound according to claim 1, wherein: it can be used for killing larva and imago of Lepidoptera, Homoptera, Coleoptera, and Orthoptera.
7. A nicotinic compound according to claim 1, wherein: can be used together with other polyesters, nicotinoids and organic sulfur compounds.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014063642A1 (en) * 2012-10-25 2014-05-01 中国中化股份有限公司 Substituted pyrimidine compound and uses thereof
WO2014139190A1 (en) * 2013-03-11 2014-09-18 山东省联合农药工业有限公司 Nicotine compound, and preparation method and usage thereof
CN106674194A (en) * 2016-12-14 2017-05-17 山东省联合农药工业有限公司 Novel-structure nicotine insecticide, and preparation method and application thereof
CN108148067A (en) * 2018-01-24 2018-06-12 邯郸市赵都精细化工有限公司 A kind of preparation method of penoxsuam

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057440A1 (en) * 1981-01-29 1982-08-11 Sankyo Company Limited Aminopyrimidine derivatives, processes for their preparation, and fungicidal, insecticidal and acaricidal compositions containing them
JPH08291149A (en) * 1995-04-21 1996-11-05 Ube Ind Ltd 4-(2-(trifuluoroalkoxy-substituted phenyl) ethylamino)pyrimidine derivative, its production and pest control agent for agriculture and horticulture
US5925644A (en) * 1996-11-15 1999-07-20 Hoechst Schering Agrevo Gmbh Substituted nitrogen heterocycles, processes for their preparation and their use as pesticides
US20020082454A1 (en) * 2000-12-27 2002-06-27 Albrecht Marhold Process for preparing 2-(4-trifluoromethoxyphenyl)ethylamine and 4-bromomethyl-and 4-chloromethyl-1-trifluoromethoxybenzene

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103232434B (en) * 2013-03-11 2015-09-16 山东省联合农药工业有限公司 A kind of nicotine compound and its production and use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0057440A1 (en) * 1981-01-29 1982-08-11 Sankyo Company Limited Aminopyrimidine derivatives, processes for their preparation, and fungicidal, insecticidal and acaricidal compositions containing them
JPH08291149A (en) * 1995-04-21 1996-11-05 Ube Ind Ltd 4-(2-(trifuluoroalkoxy-substituted phenyl) ethylamino)pyrimidine derivative, its production and pest control agent for agriculture and horticulture
US5925644A (en) * 1996-11-15 1999-07-20 Hoechst Schering Agrevo Gmbh Substituted nitrogen heterocycles, processes for their preparation and their use as pesticides
US20020082454A1 (en) * 2000-12-27 2002-06-27 Albrecht Marhold Process for preparing 2-(4-trifluoromethoxyphenyl)ethylamine and 4-bromomethyl-and 4-chloromethyl-1-trifluoromethoxybenzene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HERMAN GERSHON, ET AL.: "Pyrimidines. 6. 6-Trifluoromethyl Chloropyrimidines and Related Compounds", 《J. HETEROCYCLIC CHEM.》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014063642A1 (en) * 2012-10-25 2014-05-01 中国中化股份有限公司 Substituted pyrimidine compound and uses thereof
CN104684900A (en) * 2012-10-25 2015-06-03 中国中化股份有限公司 Substituted pyrimidine compound and uses thereof
CN104684900B (en) * 2012-10-25 2017-04-12 沈阳中化农药化工研发有限公司 Substituted pyrimidine compound and uses thereof
US9770026B2 (en) 2012-10-25 2017-09-26 Shenyang Sinochem Agrochemicals R&D Co., Ltd. Substituted pyrimidine compound and uses thereof
WO2014139190A1 (en) * 2013-03-11 2014-09-18 山东省联合农药工业有限公司 Nicotine compound, and preparation method and usage thereof
CN106674194A (en) * 2016-12-14 2017-05-17 山东省联合农药工业有限公司 Novel-structure nicotine insecticide, and preparation method and application thereof
CN106674194B (en) * 2016-12-14 2019-03-05 山东省联合农药工业有限公司 A kind of nicotinic insecticide of structure novel and its preparation method and application
CN108148067A (en) * 2018-01-24 2018-06-12 邯郸市赵都精细化工有限公司 A kind of preparation method of penoxsuam

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