CN103232434B - A kind of nicotine compound and its production and use - Google Patents

A kind of nicotine compound and its production and use Download PDF

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Publication number
CN103232434B
CN103232434B CN201310091828.8A CN201310091828A CN103232434B CN 103232434 B CN103232434 B CN 103232434B CN 201310091828 A CN201310091828 A CN 201310091828A CN 103232434 B CN103232434 B CN 103232434B
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CN103232434A (en
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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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    • 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
    • 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
    • C07D417/14—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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Agronomy & Crop Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pyridine Compounds (AREA)

Abstract

The invention provides a kind of nicotine compound and its production and use, the general structure of nicotine compound is as shown in I:

Description

A kind of nicotine compound and its production and use
Technical field
The invention belongs to field of pesticides, especially relate to a kind of nicotine compound and its production and use.
Background technology
In modern agricultural production, cause the excessive use of agricultural chemicals for ensureing the production of farm crop, various disease and pest is developed immunity to drugs.The killing rate of existing sterilant to insect reduces greatly.The interim resistance problem discussing the maximum pesticide imidacloprid of current usage quantity of " Chinese agronomy circular " the 22nd volume the 1st, capillary dropping is utilized to determine the regional insect in four, Shandong to the resistance level of Provado, find the resistance to Provado all created in various degree, wherein, the resistant multiple of Distributions in Liaocheng of Shandong Province population is 9.6 times.
Therefore, research and develop a kind of novel, insecticidal activity is high, the sterilant that not easily develops immunity to drugs solves current insect to the inexorable trend of the resistance problems of existing sterilant.
Summary of the invention
The object of the invention is, for above-mentioned problems of the prior art, to provide a kind of nicotine compound and its production and use, this nicotine compound is used for sterilant and has the advantages that insecticidal activity by force, not easily develops immunity to drugs.
For achieving the above object, the technical scheme adopted is in the present invention: a kind of nicotine compound, has the general structure as shown in I:
，
Wherein,
R 1be selected from the one in trifluoromethyl, 2,2,2-trifluoroethyls, 2,2-bis-fluoro ethyls, 2-base-3-chloro-5-trifluoromethylpyridine, 2-base-5-5-flumethiazine, 3,4,4-tri-fluoro-3-butenyls;
R 2be selected from 2-chloro-5-methylene pyridine or 2-chloro-5-methylene radical thiazole;
R 3be selected from methyl, ethyl, the one in n-propyl.
A preparation method for nicotine compound, comprises the following steps:
1. 1mol phenol is dissolved in 500-800ml N, in dinethylformamide, add 1-5mol salt of wormwood, at 40-100 DEG C, stir 1-10h, then 1mol compd A is added, at 50-100 DEG C, react 1-24 hour, steam solvent after reaction terminates, add water and methylene dichloride extracts, get solvent layer, steam solvent, obtain intermediate II, reaction formula is as follows:
；
2. the intermediate II of 1mol is dissolved in the alcohol solution of 500-800ml 50%, add 1-1.05mol paraformaldehyde and the sodium cyanide with paraformaldehyde equivalent, 1-24h is reacted at 30-60 DEG C, after reaction terminates, add methylene dichloride to extract, get solvent layer, steam solvent, column chromatography for separation obtains intermediate III, and reaction formula is as follows:
；
3. the compd B of 1mol is dissolved in 300-2000ml methyl alcohol, then the thiocarbamide of 1-5mol and the sodium methylate with thiocarbamide equivalent is added, back flow reaction 8-24h, room temperature is down to after reaction, salt acid for adjusting pH is to 5-6, the crystal of precipitation is joined in 300-2000ml ammoniacal liquor, add 0.05g Raney's nickel, back flow reaction 1-8h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then the phosphorus pentachloride with thiocarbamide equivalent is added, back flow reaction 1-24h, the liquid caustic soda of 30% regulates pH to 5-6, branch vibration layer, steam solvent, obtain intermediate IV, reaction formula is as follows:
；
4. dissolve in a solvent by the intermediate IV of 1mol and 1mol intermediate III, add 1-10mol alkali, react 1-24h at 25-125 DEG C, reaction terminates rear filtration, steams solvent, and column chromatography for separation obtains intermediate V, and reaction formula is as follows:
；
5. 1mol intermediate V and 1mol Compound C are dissolved in a solvent, add 1-10mol alkali, at 25-150 DEG C, react 1-24h, reaction terminates rear filtration, steams solvent, and column chromatography for separation obtains nicotine compound I, and reaction formula is as follows:
；
Wherein, in compd A, B, C:
R 1be selected from the one in trifluoromethyl, 2,2,2-trifluoroethyls, 2,2-bis-fluoro ethyls, 2-base-3-chloro-5-trifluoromethylpyridine, 2-base-5-5-flumethiazine, 3,4,4-tri-fluoro-3-butenyls;
R 2be selected from 2-chloro-5-methylene pyridine or 2-chloro-5-methylene radical thiazole;
R 3be selected from methyl, ethyl, the one in n-propyl.
A preparation method for nicotine compound, step 4. with step 5. described in solvent can be one in methyl alcohol, ethanol, Virahol, butanols, DMF; Step 4. with step 5. described in alkali can be one in sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium tert-butoxide, potassium tert.-butoxide, salt of wormwood, sodium carbonate.
A preparation method for nicotine compound, comprises the following steps:
1. 1mol phenol is dissolved in 500-800ml N, in dinethylformamide, add 1-2mol salt of wormwood, at 60-80 DEG C, stir 3-5h, then 1mol compd A is added, at 60-80 DEG C, react 3-4h, steam solvent after reaction terminates, add 500ml water and 500ml methylene dichloride extracts, get solvent layer, steam solvent, obtain intermediate II, reaction formula is as follows:
；
2. the intermediate II of 1mol is dissolved in the aqueous ethanolic solution of 500-800ml 50%, add 1-1.05mol paraformaldehyde and the sodium cyanide with paraformaldehyde equivalent, 6-10h is reacted at 45-50 DEG C, after reaction terminates, add 500ml methylene dichloride to extract, get solvent layer, steam solvent, column chromatography for separation obtains intermediate III, and reaction formula is as follows:
；
3. the compd B of 1mol is dissolved in 500-800ml methyl alcohol, then the thiocarbamide of 1-1.05mol and the sodium methylate with thiocarbamide equivalent is added, back flow reaction 8-10h, room temperature is down to after reaction, salt acid for adjusting pH is to 5-6, the crystal of precipitation is joined in 300-2000ml ammoniacal liquor, add 0.05g Raney's nickel, back flow reaction 1-8h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then the phosphorus pentachloride with thiocarbamide equivalent is added, back flow reaction 6-8h, the liquid caustic soda of 30% regulates pH to 5-6, branch vibration layer, steam solvent, obtain intermediate IV, reaction formula is as follows:
；
4. be dissolved in DMF by the intermediate IV of 1mol and 1mol intermediate III, add 1-2mol salt of wormwood, react 4-6h at 60-80 DEG C, reaction terminates rear filtration, steams solvent, and column chromatography for separation obtains intermediate V, and reaction formula is as follows:
；
5. be dissolved in DMF by 1mol intermediate V and 1mol Compound C, add 1-2mol salt of wormwood, at 60-80 DEG C, react 4-6h, reaction terminates rear filtration, steams solvent, and column chromatography for separation obtains nicotine compound I, and reaction formula is as follows:
；
Wherein, in compd A, B, C:
R 1be selected from the one in trifluoromethyl, 2,2,2-trifluoroethyls, 2,2-bis-fluoro ethyls, 2-base-3-chloro-5-trifluoromethylpyridine, 2-base-5-5-flumethiazine, 3,4,4-tri-fluoro-3-butenyls;
R 2be selected from 2-chloro-5-methylene pyridine or 2-chloro-5-methylene radical thiazole;
R 3be selected from methyl, ethyl, the one in n-propyl.
A kind of nicotine compound of the present invention is preparing the purposes in sterilant.
A kind of nicotine compound of the present invention, for killing lepidopteran, Homoptera, Coleoptera, the larva of Orthoptera and adult.
A kind of nicotine compound of the present invention, can with other polyester, nicotinoids, the composite use of organosulfur compounds.
A kind of nicotine compound of the present invention contains multiple active group such as fluoro-containing group, pyrimidine ring, when using as sterilant, interior absorption is high, plant osmosis is good, thus has the advantage that insecticidal activity is high, insecticidal spectrum extensively, not easily develops immunity to drugs, Environmental compatibility is high.
The preparation method of a kind of nicotine compound of the present invention, the nicotine compound with general structure I is synthesized by progressively synthetic intermediate II, III, IV, V is final, technical process is simple, easy to operate, product purity is high, non-environmental-pollution, and the yield of final nicotine compound is up to 97%.
A kind of nicotine compound of the present invention has the restraining effect to insect respiratory metabolism, can the mitochondrial breathing of transfer transport between T suppression cell pigment b and c1, it is again the acting body of nAChR ligands simultaneously, interference pest movements neural system, to be played target organisms by the mode of tagging and kill prevention effect, killing rate is up to 100%.
A kind of nicotine compound of the present invention without cross resistance to the existing sterilant of lepidopteran, Homoptera, Coleoptera, orthoptera pest, has equally the insect developed immunity to drugs and kills activity preferably.The environmental pollution caused guarantee secure agricultural production, raising grain yield, prevention and elimination of disease and pests, reduction agricultural chemicals as the sterilant that activeconstituents is prepared by a kind of nicotine compound of the present invention is particularly important.
Embodiment
A kind of nicotine compound of the present invention, has the general structure as shown in I:
，
Wherein,
R 1be selected from the one in trifluoromethyl, 2,2,2-trifluoroethyls, 2,2-bis-fluoro ethyls, 2-base-3-chloro-5-trifluoromethylpyridine, 2-base-5-5-flumethiazine, 3,4,4-tri-fluoro-3-butenyls;
R 2be selected from 2-chloro-5-methylene pyridine or 2-chloro-5-methylene radical thiazole;
R 3be selected from methyl, ethyl, the one in n-propyl.
The particular compound represented by general structure of a kind of nicotine compound I of the present invention is as shown in the table:
Nicotine compound Structural formula
（1）
（2）
（3）
（4）
（5）
（6）
（7）
（8）
（9）
（10）
（11）
（12）
（13）
（14）
（15）
（16）
（17）
（18）
（19）
（20）
（21）
（22）
（23）
（24）
（25）
（26）
（27）
（28）
（29）
（30）
（31）
（32）
（33）
（34）
（35）
（36）
The preparation method of a kind of nicotine compound of the present invention, comprises the following steps:
1. 1mol phenol is dissolved in 500-800ml N, in dinethylformamide, add 1-5mol salt of wormwood, at 40-100 DEG C, stir 1-10h, then 1mol compd A is added, at 50-100 DEG C, react 1-24 hour, steam solvent after reaction terminates, add water and methylene dichloride extracts, get solvent layer, steam solvent, obtain intermediate II, reaction formula is as follows:
2. the intermediate II of 1mol is dissolved in the alcohol solution of 500-800ml 50%, add 1-1.05mol paraformaldehyde and the sodium cyanide with paraformaldehyde equivalent, 1-24h is reacted at 30-60 DEG C, after reaction terminates, add methylene dichloride to extract, get solvent layer, steam solvent, column chromatography for separation obtains intermediate III, and reaction formula is as follows:
；
3. the compd B of 1mol is dissolved in 300-2000ml methyl alcohol, then the thiocarbamide of 1-5mol and the sodium methylate with thiocarbamide equivalent is added, back flow reaction 8-24h, room temperature is down to after reaction, salt acid for adjusting pH is to 5-6, the crystal of precipitation is joined in 300-2000ml ammoniacal liquor, add 0.05g Raney's nickel, back flow reaction 1-8h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then the phosphorus pentachloride with thiocarbamide equivalent is added, back flow reaction 1-24h, the liquid caustic soda of 30% regulates pH to 5-6, branch vibration layer, steam solvent, obtain intermediate IV, reaction formula is as follows:
；
4. dissolve in a solvent by the intermediate IV of 1mol and 1mol intermediate III, add 1-10mol alkali, react 1-24h at 25-125 DEG C, reaction terminates rear filtration, steams solvent, and column chromatography for separation obtains intermediate V, and reaction formula is as follows:
；
5. 1mol intermediate V and 1mol Compound C are dissolved in a solvent, add 1-10mol alkali, at 25-150 DEG C, react 1-24h, reaction terminates rear filtration, steams solvent, and column chromatography for separation obtains nicotine compound I, and reaction formula is as follows:
Wherein, in compd A, B, C:
R 1be selected from the one in trifluoromethyl, 2,2,2-trifluoroethyls, 2,2-bis-fluoro ethyls, 2-base-3-chloro-5-trifluoromethylpyridine, 2-base-5-5-flumethiazine, 3,4,4-tri-fluoro-3-butenyls;
R 2be selected from 2-chloro-5-methylene pyridine or 2-chloro-5-methylene radical thiazole;
R 3be selected from methyl, ethyl, the one in n-propyl.
Preferred technical scheme is:
A preparation method for nicotine compound, step 4. with step 5. described in solvent can be one in methyl alcohol, ethanol, Virahol, butanols, DMF; Step 4. with step 5. described in alkali can be one in sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, sodium tert-butoxide, potassium tert.-butoxide, salt of wormwood, sodium carbonate.The solvability of preferred solvent to reactant is higher, is conducive to the carrying out reacted.Preferred alkali can provide suitable reaction environment, and the by product after simultaneously making reaction easily removes.
A preparation method for nicotine compound, comprises the following steps:
1. 1mol phenol is dissolved in 500-800ml N, in dinethylformamide, add 1-2mol salt of wormwood, at 60-80 DEG C, stir 3-5h, then 1mol compd A is added, at 60-80 DEG C, react 3-4h, steam solvent after reaction terminates, add 500ml water and 500ml methylene dichloride extracts, get solvent layer, steam solvent, obtain intermediate II, reaction formula is as follows:
；
2. the intermediate II of 1mol is dissolved in the aqueous ethanolic solution of 500-800ml 50%, add 1-1.05mol paraformaldehyde and the sodium cyanide with paraformaldehyde equivalent, 6-10h is reacted at 45-50 DEG C, after reaction terminates, add 500ml methylene dichloride to extract, get solvent layer, steam solvent, column chromatography for separation obtains intermediate III, and reaction formula is as follows:
；
3. the compd B of 1mol is dissolved in 500-800ml methyl alcohol, then the thiocarbamide of 1-1.05mol and the sodium methylate with thiocarbamide equivalent is added, back flow reaction 8-10h, room temperature is down to after reaction, salt acid for adjusting pH is to 5-6, the crystal of precipitation is joined in 300-2000ml ammoniacal liquor, add 0.05g Raney's nickel, back flow reaction 1-8h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then the phosphorus pentachloride with thiocarbamide equivalent is added, back flow reaction 6-8h, the liquid caustic soda of 30% regulates pH to 5-6, branch vibration layer, steam solvent, obtain intermediate IV, reaction formula is as follows:
；
4. be dissolved in DMF by the intermediate IV of 1mol and 1mol intermediate III, add 1-2mol salt of wormwood, react 4-6h at 60-80 DEG C, reaction terminates rear filtration, steams solvent, and column chromatography for separation obtains intermediate V, and reaction formula is as follows:
；
5. be dissolved in DMF by 1mol intermediate V and 1mol Compound C, add 1-2mol salt of wormwood, at 60-80 DEG C, react 4-6h, reaction terminates rear filtration, steams solvent, and column chromatography for separation obtains nicotine compound I, and reaction formula is as follows:
Wherein, in compd A, B, C:
R 1be selected from the one in trifluoromethyl, 2,2,2-trifluoroethyls, 2,2-bis-fluoro ethyls, 2-base-3-chloro-5-trifluoromethylpyridine, 2-base-5-5-flumethiazine, 3,4,4-tri-fluoro-3-butenyls;
R 2be selected from 2-chloro-5-methylene pyridine or 2-chloro-5-methylene radical thiazole;
R 3be selected from methyl, ethyl, the one in n-propyl.
A kind of nicotine compound of the present invention is preparing the purposes in sterilant.Can be used as active ingredient and jointly form sterilant with agriculturally acceptable carrier, the weight percentage of biocidal activity component is 0.5-90%.The formulation of sterilant can be dry powder, visual pulvis, missible oil, microemulsion, paste, granule, solution, suspension agent, is prepared from according to currently known methods.
A kind of nicotine compound of the present invention, for killing lepidopteran, Homoptera, Coleoptera, the larva of Orthoptera and adult.
A kind of nicotine compound of the present invention, can with other polyester, nicotinoids, the composite use of organosulfur compounds, to reach synergistic function, composite weight ratio is 1:20-20:1.
A kind of nicotine compound of the present invention and preparation method thereof, according to particular compound in table, can have following specific embodiment:
The preparation process of embodiment 1 nicotine compound (1) is as follows:
1. 1mol phenol is dissolved in 500ml N, in dinethylformamide, add 1mol salt of wormwood, at 40 DEG C, stir 10h, then add 1mol bromotrifluoromethane, react 24 hours at 50 DEG C, steam solvent after reaction terminates, add 500ml water and 500ml methylene dichloride extracts, get solvent layer, steam solvent, obtain 152.28g intermediate II;
2. 152.28g intermediate II is dissolved in the methanol aqueous solution of 500ml 50%, add at 30 DEG C 1mol paraformaldehyde and with 1mol sodium cyanide, reaction 24h, after reaction terminates, add 500ml methylene dichloride to extract, get solvent layer, steam solvent, 6:4(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 190.65g intermediate III;
3. the malonaldehydic acid ethyl ester of 1mol is dissolved in 300ml methyl alcohol, then adds thiocarbamide and the 1mol sodium methylate of 1mol, back flow reaction 8h, be down to room temperature after reaction, the crystal of precipitation, to 5, joins in 300ml ammoniacal liquor by salt acid for adjusting pH, add 0.05g Raney's nickel, back flow reaction 1h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then adds 1mol phosphorus pentachloride, back flow reaction 1h, the liquid caustic soda of 30% regulates pH to 5, branch vibration layer, steams solvent, obtains 149.04g intermediate IV;
4. the intermediate IV of 149.04g and 190.65g intermediate III are dissolved in methyl alcohol, add 1mol sodium carbonate, react 24h at 25 DEG C, reaction terminates rear filtration, steams solvent, 8:2(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 297.9g intermediate V;
5. 297.9g intermediate V and 1mol2-chlorine-5-chloromethyl pyridine are dissolved in methyl alcohol, add 1mol sodium carbonate, at 25 DEG C, react 24h, reaction terminates rear filtration, steams solvent, 7:3(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 405.84g nicotine compound (1), yield is 89%, Elemental analysis data: C:52.53%, H:3.75%, Cl:15.51%, F:12.46%, N:12.25%, O:3.50%.
The preparation process of embodiment 2 nicotine compound (8) is as follows:
1. 1mol phenol is dissolved in 500ml N, in dinethylformamide, add 5mol salt of wormwood, at 100 DEG C, stir 1h, then add 1mol 1-Halothane, react 1 hour at 100 DEG C, steam solvent after reaction terminates, add 500ml water and 500ml methylene dichloride extracts, get solvent layer, steam solvent, obtain 170.72g intermediate II;
2. 170.72g intermediate II is dissolved in the aqueous propanol solution of 800ml 50%, add at 60 DEG C 1.05mol paraformaldehyde and with 1.05mol sodium cyanide, reaction 1h, after reaction terminates, add 500ml methylene dichloride to extract, get solvent layer, steam solvent, 6:4(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 210.24g intermediate III;
3. the methyl aceto acetate of 1mol is dissolved in 2000ml methyl alcohol, then thiocarbamide and the 5mol sodium methylate of 5mol is added, back flow reaction 24h, room temperature is down to after reaction, salt acid for adjusting pH is to 6, the crystal of precipitation is joined in 2000ml ammoniacal liquor, adds 0.05g Raney's nickel, back flow reaction 24h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then adds 5mol phosphorus pentachloride, back flow reaction 24h, the liquid caustic soda of 30% regulates pH to 6, branch vibration layer, steams solvent, obtains 167.2g intermediate IV;
4. the intermediate IV of 167.2g and 210.24g intermediate III are dissolved in butanols, add 10mol sodium hydroxide, react 1h at 125 DEG C, reaction terminates rear filtration, steams solvent, 8:2(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 337.46g intermediate V;
5. 337.46g intermediate V and 1mol CCMP are dissolved in butanols, add 10mol sodium hydroxide, at 150 DEG C, react 1h, reaction terminates rear filtration, steams solvent, 7:3(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 450.12g nicotine compound (8), yield is 93%, Elemental analysis data: C:54.44%, H:4.36%, Cl:14.61%, F:11.74%, N:11.54%, O:3.30%.
The preparation process of embodiment 3 nicotine compound (11) is as follows:
1. 1mol phenol is dissolved in 500ml N, in dinethylformamide, add 2mol salt of wormwood, at 80 DEG C, stir 5h, then add 1mol 2-chloro-5-trifluoromethylpyridine, react 4 hours at 80 DEG C, steam solvent after reaction terminates, add 500ml water and 500ml methylene dichloride extracts, get solvent layer, steam solvent, obtain 236.61g intermediate II;
2. 236.61g intermediate II is dissolved in the aqueous ethanolic solution of 600ml 50%, add at 50 DEG C 1.05mol paraformaldehyde and with 1.05mol sodium cyanide, reaction 10h, after reaction terminates, add 500ml methylene dichloride to extract, get solvent layer, steam solvent, 6:4(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 276.36g intermediate III;
3. the methyl aceto acetate of 1mol is dissolved in 800ml methyl alcohol, then thiocarbamide and the 1.05mol sodium methylate of 1.05mol is added, back flow reaction 10h, room temperature is down to after reaction, salt acid for adjusting pH is to 6, the crystal of precipitation is joined in 700ml ammoniacal liquor, adds 0.05g Raney's nickel, back flow reaction 24h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then adds 1.05mol phosphorus pentachloride, back flow reaction 8h, the liquid caustic soda of 30% regulates pH to 5, branch vibration layer, steams solvent, obtains 170.72g intermediate IV;
4. the intermediate IV of 170.72g and 276.36g intermediate III are dissolved in N, in dinethylformamide, add 2mol salt of wormwood, at 80 DEG C, react 6h, reaction terminates rear filtration, steams solvent, 8:2(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 409.34g intermediate V;
5. 409.34g intermediate V and 1mol CCMP are dissolved in DMF, add 2mol salt of wormwood, 6h is reacted at 80 DEG C, reaction terminates rear filtration, steams solvent, 7:3(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 530.59g nicotine compound (11), yield is 97%, Elemental analysis data: C:56.94%, H:4.04%, Cl:12.93%, F:10.39%, N:12.77%, O:2.92%.
The preparation process of embodiment 4 nicotine compound (24) is as follows:
1. 1mol phenol is dissolved in 600ml N, in dinethylformamide, add 1.5mol salt of wormwood, at 70 DEG C, stir 4h, then add the bromo-4-trifluorobutene of 1mol 1-, react 3.5 hours at 70 DEG C, steam solvent after reaction terminates, add 500ml water and 500ml methylene dichloride extracts, get solvent layer, steam solvent, obtain 193.92g intermediate II;
2. 193.92g intermediate II is dissolved in the aqueous ethanolic solution of 500ml 50%, add at 48 DEG C 1.02mol paraformaldehyde and with 1.02mol sodium cyanide, reaction 8h, after reaction terminates, add 500ml methylene dichloride to extract, get solvent layer, steam solvent, 6:4(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 235.2g intermediate III;
3. the malonaldehydic acid ethyl ester of 1mol is dissolved in 750ml methyl alcohol, then thiocarbamide and the 1.02mol sodium methylate of 1.02mol is added, back flow reaction 9h, room temperature is down to after reaction, salt acid for adjusting pH is to 6, the crystal of precipitation is joined in 1000ml ammoniacal liquor, adds 0.05g Raney's nickel, back flow reaction 4h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then adds 1.02mol phosphorus pentachloride, back flow reaction 7h, the liquid caustic soda of 30% regulates pH to 6, branch vibration layer, steams solvent, obtains 155.2g intermediate IV;
4. the intermediate IV of 155.2g and 235.2g intermediate III are dissolved in N, in dinethylformamide, add 1.05mol salt of wormwood, at 70 DEG C, react 5h, reaction terminates rear filtration, steams solvent, 8:2(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 354.31g intermediate V;
5. 354.31g intermediate V and 1mol 2-chloro-5-chloromethyl thiazole are dissolved in DMF, add 1.5mol salt of wormwood, at 70 DEG C, react 5h, reaction terminates rear filtration, steams solvent, 7:3(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 476.9g nicotine compound (24), yield is 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%.
The preparation process of embodiment 5 nicotine compound (33) is as follows:
1. 1mol phenol is dissolved in 500ml N, in dinethylformamide, add 1mol salt of wormwood, at 60 DEG C, stir 3h, then add 1mol 1-difluoro monobromethane, react 3 hours at 60 DEG C, steam solvent after reaction terminates, add 500ml water and 500ml methylene dichloride extracts, get solvent layer, steam solvent, obtain 156.42g intermediate II;
2. 156.42g intermediate II is dissolved in the aqueous ethanolic solution of 800ml 50%, add at 45 DEG C 1.05mol paraformaldehyde and with 1.05mol sodium cyanide, reaction 6h, after reaction terminates, add 500ml methylene dichloride to extract, get solvent layer, steam solvent, 6:4(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 194.97g intermediate III;
3. the positive Propionylacetic acid ethyl ester of 1mol is dissolved in 500ml methyl alcohol, then thiocarbamide and the 1mol sodium methylate of 1mol is added, back flow reaction 8h, room temperature is down to after reaction, salt acid for adjusting pH is to 5, the crystal of precipitation is joined in 2000ml ammoniacal liquor, adds 0.05g Raney's nickel, back flow reaction 24h, filter, decrease temperature crystalline, by dissolution of crystals in 1000ml toluene, then adds 1mol phosphorus pentachloride, back flow reaction 6h, the liquid caustic soda of 30% regulates pH to 6, branch vibration layer, steams solvent, obtains 182.4g intermediate IV;
4. the intermediate IV of 182.4g and 194.97g intermediate III are dissolved in Virahol, add 1mol salt of wormwood, react 4h at 60 DEG C, reaction terminates rear filtration, steams solvent, 8:2(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 340.8g intermediate V;
5. 340.8g intermediate V and chloro-5 5-chloromethyl thiazoles of 1mol 2-are dissolved in butanols, add 1mol sodium hydroxide, at 60 DEG C, react 4h, reaction terminates rear filtration, steams solvent, 7:3(volume ratio) ethyl acetate/petroleum ether column chromatography for separation obtain 466.56g nicotine compound (33), yield is 96%, Elemental analysis data: C:51.75%, H:4.55%, Cl:14.55%, F:7.80%, N:11.50%, O:3.28%, S:6.58%.
Biological examples:
The nicotine compound represented with formula I likely compound be the formulated sterilant of activeconstituents, contrast with existing sterilant:
Embodiment 1 small heart-eating peach worm (lepidopteran) is tested:
Solvent: the dimethyl formamide of 7 parts of weight;
Emulsifying agent: the alkylaryl polyglycol ether of 1 part of weight;
Activeconstituents: the compound (1) of 1 part of weight;
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and small heart-eating peach worm is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 7 days prevention effect (%) after medicine
Compound (1) 30 98%
Effective cypermethrin 30 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (1) is apparently higher than effective cypermethrin.
Embodiment 2 smaller apple leafrol-ler (lepidopteran) is tested
Solvent: the dimethyl sulfoxide (DMSO) of 7 parts of weight
Emulsifying agent: the alkylaryl polyglycol ether of 2 parts of weight
Activeconstituents: the compound (2) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and smaller apple leafrol-ler is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (2) 50 100%
Trichlorphon 50 85%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (2) is apparently higher than Trichlorphon.
Embodiment 3 bollworm (lepidopteran) is tested
Solvent: the dimethyl sulfoxide (DMSO) of 7 parts of weight
Emulsifying agent: the alkylaryl polyglycol ether of 2 parts of weight
Activeconstituents: the compound (3) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and bollworm is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (3) 30 100%
Effective cypermethrin 30 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (3) is apparently higher than effective cypermethrin.
Embodiment 4 small cabbage moth (lepidopteran) is tested
Solvent: the dimethyl sulfoxide (DMSO) of 7 parts of weight
Emulsifying agent: the alkylaryl polyglycol ether of 2 parts of weight
Activeconstituents: the compound (4) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and small cabbage moth is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (4) 30 99%
Avrmectin 30 89%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (4) is apparently higher than Avrmectin.
Embodiment 5 black cutworm (lepidopteran) is tested
Solvent: 8 parts of weight dimethyl sulfoxide (DMSO)
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (5) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and black cutworm is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (5) 30 100%
Chlorpyrifos 94 30 85%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (5) is apparently higher than Chlorpyrifos 94.
Embodiment 6 prodenia litura (lepidopteran) is tested
Solvent: 8 parts of weight dimethyl sulfoxide (DMSO)
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (6) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and prodenia litura is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (6) 50 100%
Chlorpyrifos 94 50 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (6) is apparently higher than Chlorpyrifos 94.
Embodiment 7 beet armyworm (lepidopteran) is tested
Solvent: 8 parts of weight acetones
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (7) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and beet armyworm is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 7 days prevention effect (%) after medicine
Compound (7) 30 95%
Avrmectin 30 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (7) is apparently higher than Avrmectin.
Embodiment 8 striped rice borer (lepidopteran) is tested
Solvent: 8 parts of weight acetones
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (8) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and striped rice borer is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (8) 30 100%
Cartap 30 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (8) is apparently higher than cartap.
Embodiment 9 bean-pod borer (lepidopteran) is tested
Solvent: 8 parts of weight acetones
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (9) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and bean-pod borer is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (9) 30 100%
Cypermethrin 30 87%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (9) is apparently higher than Cypermethrin.
Embodiment 10 Pyrausta nubilalis (Hubern). (lepidopteran) is tested
Solvent: 7 parts of weight dimethyl sulfoxide (DMSO)
Emulsifying agent: 2 parts of weight alkylaryl polyglycol ethers
Activeconstituents: the compound (10) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and Pyrausta nubilalis (Hubern). is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (10) 100 100%
Cypermethrin 100 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (10) is apparently higher than Cypermethrin.
Embodiment 11 small white (lepidopteran) is tested
Solvent: 8 parts of weight acetones
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (11) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and small white is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (11) 60 95%
Nimbin extract 60 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (11) is apparently higher than nimbin extract.
Embodiment 12 tea geometrid (lepidopteran) is tested
Solvent: 8 parts of weight acetones
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (12) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and tea geometrid larvae is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 7 days prevention effect (%) after medicine
Compound (12) 100 100%
Deltamethrin 100 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (12) is apparently higher than Deltamethrin.
Embodiment 13 trialeurodes vaporariorum (Homoptera) is tested
Solvent: 8 parts of weight acetones
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (13) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and trialeurodes vaporariorum is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 5 days prevention effect (%) after medicine
Compound (13) 50 100%
Provado 50 70%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (13) is apparently higher than Provado.
Embodiment 14 small brown rice planthopper (Homoptera) is tested
Solvent: 7 parts of weight dimethyl sulfoxide (DMSO)
Emulsifying agent: 2 parts of weight alkylaryl polyglycol ethers
Activeconstituents: the compound (14) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and small brown rice planthopper is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (14) 100 100%
Diacloden 100 85%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (14) is apparently higher than Diacloden.
Embodiment 15 black peach aphid (Homoptera) is tested
Solvent: 7 parts of weight dimethyl sulfoxide (DMSO)
Emulsifying agent: 2 parts of weight alkylaryl polyglycol ethers
Activeconstituents: the compound (15) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and black peach aphid is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 5 days prevention effect (%) after medicine
Compound (15) 100 100%
Acetamiprid 100 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (15) is apparently higher than acetamiprid.
Embodiment 16 green plant bug (Homoptera) is tested
Solvent: 7 parts of weight dimethyl sulfoxide (DMSO)
Emulsifying agent: 2 parts of weight alkylaryl polyglycol ethers
Activeconstituents: the compound (16) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and green plant bug is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (16) 80 100%
Malathion 80 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (16) is apparently higher than Malathion.
Embodiment 17 chlorita biguttula (Homoptera) is tested
Solvent: 7 parts of weight dimethyl sulfoxide (DMSO)
Emulsifying agent: 2 parts of weight alkylaryl polyglycol ethers
Activeconstituents: the compound (17) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and chlorita biguttula is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 5 days prevention effect (%) after medicine
Compound (17) 60 90%
Bifenthrin 60 70%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (17) is apparently higher than bifenthrin.
Embodiment 18 straw aphid (Homoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (18) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " soaks worm, straw aphid is immersed each medicament and processes by leaf dipping method respectively, and result is as following table:
Medicament Concentration ppm 5 days prevention effect (%) after medicine
Compound (18) 60 100%
Provado 60 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (18) is apparently higher than Provado.
Embodiment 19 San Jose scale (Homoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (19) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and San Jose scale is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (19) 100 95%
Methidathion 100 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (19) is apparently higher than methidathion.
Embodiment 20 unaspis shield kuwana (Homoptera) is tested
Solvent: 9 parts of weight dimethyl sulfoxide (DMSO)
Activeconstituents: the compound (20) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and unaspis shield kuwana is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 5 days prevention effect (%) after medicine
Compound (20) 100 100%
Pyridaben 100 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (20) is apparently higher than pyridaben.
Embodiment 21 icerya purchasi (Homoptera) is tested
Solvent: 9 parts of weight dimethyl sulfoxide (DMSO)
Activeconstituents: the compound (21) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and icerya purchasi is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 5 days prevention effect (%) after medicine
Compound (21) 100 100%
Omethoate 100 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (21) is apparently higher than omethoate.
Embodiment 22 radish aphid (Homoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (22) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and radish aphid is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (22) 100 100%
Acetamiprid 100 85%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (22) is apparently higher than acetamiprid.
Embodiment 23 cotten aphid (Homoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (23) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and cotten aphid is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (23) 100 100%
Pyridaben 100 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (23) is apparently higher than pyridaben.
Embodiment 24 brown paddy plant hopper (Homoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (24) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " is soaked worm, leaf dipping method and brown paddy plant hopper is immersed respectively each medicament and process, and result is as following table:
Medicament Concentration ppm 3 days prevention effect (%) after medicine
Compound (23) 100 100%
Provado 100 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (24) is apparently higher than Provado.
Embodiment 25 wheat head ground beetle (Coleoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (25) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (25) 50 100%
Ethiprole 50 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (25) is apparently higher than ethiprole.
Embodiment 26 wireworm (Coleoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (26) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (26) 50 95%
Carbosulfan 50 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (26) is apparently higher than carbosulfan.
Embodiment 27 Callosobruchus chinensis (Coleoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (27) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (27) 50 100%
Fenitrothion 95 50 85%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (27) is apparently higher than fenitrothion 95.
Embodiment 28 striped flea-beetle (Coleoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (28) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (28) 50 100%
Chlorpyrifos 94 50 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (28) is apparently higher than Chlorpyrifos 94.
Embodiment 29 mulberry borer (Coleoptera) is tested
Solvent: 8.5 parts of acetone
Emulsifying agent: 0.5 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (29) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (29) 50 100%
Affirm (Merck Co.) 50 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (29) is apparently higher than Affirm (Merck Co.).
Embodiment 30 sitophilus zea-mais (Coleoptera) is tested
Solvent: 8 parts of acetone
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (30) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (30) 50 100%
Provado 50 80%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (30) is apparently higher than Provado.
Embodiment 31 longicorn beetle (Coleoptera) is tested
Solvent: 8 parts of acetone
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (31) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (31) 50 98%
Provado 50 85%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (31) is apparently higher than Provado.
The little buprestid beetle of embodiment 32 oranges and tangerines (Coleoptera) is tested
Solvent: 8 parts of acetone
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (32) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (32) 50 100%
Chlorpyrifos 94 50 85%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (32) is apparently higher than Chlorpyrifos 94.
Embodiment 33 weevil (Coleoptera) is tested
Solvent: 8 parts of acetone
Emulsifying agent: 1 part of weight alkylaryl polyglycol ether
Activeconstituents: the compound (33) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " oral bio assay method is tested, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (33) 50 90%
Chlorpyrifos 94 50 75%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (33) is apparently higher than Chlorpyrifos 94.
Embodiment 34 Asiatic migrotory locust (Orthoptera) is tested
Solvent: 9 parts of dimethyl sulfoxide (DMSO)
Activeconstituents: the compound (34) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " feed mixes malicious method and tests, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (34) 100 100%
Flufenoxuron 100 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (34) is apparently higher than flufenoxuron.
Embodiment 35 Chinese rice grasshopper (Orthoptera) is tested
Solvent: 9 parts of dimethyl sulfoxide (DMSO)
Activeconstituents: the compound (35) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " feed mixes malicious method and tests, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (35) 100 100%
Flufenoxuron 100 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (35) is apparently higher than flufenoxuron.
Embodiment 36 mole cricket (Orthoptera) is tested
Solvent: 9 parts of dimethyl sulfoxide (DMSO)
Activeconstituents: the compound (36) of 1 part of weight
By said components by weight mixing, be diluted to desired concn.According to national standard---" indoor bioassay test rule " soil mixes medicine and raises worm method and test, and result is as following table:
Medicament Concentration ppm 3 days mortality ratio (%) after medicine
Compound (36) 100 100%
Chlorpyrifos 94 100 90%
In table, result shows, the prevention effect of the sterilant prepared for activeconstituents with compound (36) is apparently higher than Chlorpyrifos 94.

Claims (2)

1. a nicotine compound, is characterized in that: have the general structure as shown in I:
Wherein,
R 1be selected from 3-chloro-5-trifluoromethylpyridine-2-base or 5-5-flumethiazine-2-base;
R 2be selected from 2-chloropyridine-5-methylene radical or 2-diuril azoles-5-methylene radical;
R 3be selected from the one in methyl, ethyl, n-propyl.
2. the purposes of a kind of nicotine compound according to claim 1, is characterized in that: for killing lepidopteran, Homoptera, Coleoptera, the larva of Orthoptera and adult.
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