CN103724324A - Imidacloprid-like ramification and preparing method thereof - Google Patents
Imidacloprid-like ramification and preparing method thereof Download PDFInfo
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- CN103724324A CN103724324A CN201310683741.XA CN201310683741A CN103724324A CN 103724324 A CN103724324 A CN 103724324A CN 201310683741 A CN201310683741 A CN 201310683741A CN 103724324 A CN103724324 A CN 103724324A
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- provado
- derivative
- ramification
- imidacloprid
- methyl
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- 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
- C07D401/06—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 carbon chain containing only aliphatic carbon atoms
Abstract
The invention discloses an imidacloprid-like ramification and a preparing method thereof, and belongs to the technical field of pesticide preparation. The ramification is 1-(4-chlorin-3-methylpyridine)-N-nitroimidazolidine-2-amine. The preparing method thereof comprises the following steps: firstly, dissolving superfluous 2-nitroaminoimidazoline by acetonitrile at a normal temperature; adding sodium hydride as an acid-binding agent and uniformly mixing; stirring and dripping the acetonitrile solution containing 4-chlorin-3-methyl-2-CCMP; then flowing back at the temperature of 90 DEG C for 5 h after dripping; removing the acetonitrile solvent after distillation at reduced pressure and dissolving with water; extracting through dichloromethane or chloroform; obtaining the coarse product of imidacloprid-like ramification after drying and concentrating the organic layer; preparing the pure product of the imidacloprid-like ramification after column chromatography separation on silica gel. The imidacloprid-like ramification and the preparing method have the advantages that the raw materials are easily obtained, the price is low, the cost is low, the medicinal effect of the product is excellent and the like.
Description
Technical field
the invention belongs to sterilant preparing technical field, be specifically related to kind Provado derivative and preparation method thereof.
Background technology
provado is nicotinoids ultra-high efficiency sterilant, has developed at present the large sterilant of the first in the world.Imidacloprid Insecticide has the characteristics such as wide spectrum, efficient, low toxicity, low residue and insect are difficult for developing immunity to drugs, because it has good security features to people, animal, plant and natural enemy, Provado just progressively replaces hypertoxic organophosphorus insecticide, becomes one of key variety of China and even World Key development.
from the structural formula of Provado, current synthetic method is CCMP (CCMP) and the condensation of 2-nitro imido imidazolyl alkane at present.For 2-nitro imido imidazolyl alkane, the synthetic method of existing economical and efficient, but CCMP is still relatively difficult to obtain, and for the synthetic and technical study of this compound, is never interrupted, and the corresponding achievement of delivering is also a lot.Wherein comparatively typical, as document " the DL-oxysuccinic acid of employing is that raw material is prepared CCMP " (< < chemistry world > >, 2000,41 (4): 205-208) in disclosed preparation method, the total recovery of CCMP only has 18%; Document " adopts CMP to prepare CCMP " (Chemical Engineering Journal, 2003,95,33 – 36), and reaction needed is used expensive Palladous chloride and hypertoxic chlorine, and productive rate is the highest, also only has 60%; Current most of manufacturing enterprise adopts cyclopentadiene cyclization method, although dropped into large-scale commercial production, its result does not allow people satisfied all the time.
the present invention, from another one thinking, chooses some chloromethylpyridine derivatives of comparatively easily preparing and replaces CCMP, with the condensation of 2-nitro imido imidazolyl alkane, prepares the chemically modified product of Provado.By the active testing to new compound, to finding one with low cost, and possesses or exceedes the new compound of Provado drug effect.
Summary of the invention
the present invention, for solving the problems of the technologies described above, provides kind Provado derivative and preparation method thereof.
a kind Provado derivative provided by the present invention is the chloro-3-picoline of 1-(4-methyl)-N-nitroimidazole alkane-2-base amine, the structural formula of such Provado derivative is:
the structural similitude of such Provado derivative and Provado is only position and the many methyl substituents that has changed chlorine and chloromethyl on pyridine ring.
the preparation method of such Provado derivative that the present invention carries is specific as follows:
under normal temperature, in reactor, excessive 2-nitro imido imidazolyl alkane is dissolved with acetonitrile, add sodium hydride to make acid binding agent, mix, stir the acetonitrile solution of the chloro-3-methyl-2-of the lower 4-of dropping chloromethylpyridine, dropwise rear 90 ℃ of backflow 5h, tlc (TLC) detection reaction is complete, acetonitrile solvent is removed in underpressure distillation, then be dissolved in water, with methylene dichloride or chloroform extraction, the dry concentrated crude product that makes such Provado derivative of organic layer, it is separated with silica gel column chromatography, make the sterling of such Provado derivative.
the amount of substance ratio of the chloro-3-methyl-2-of described 2-nitro imido imidazolyl alkane and 4-chloromethylpyridine is: (1.1 ~ 1.5): 1; The mass ratio of described sodium hydride and 2-nitro imido imidazolyl alkane is: (1.1 ~ 1.3): 1.
in this preparation method, the synthetic method of 2-chloromethyl-3-methyl-4-chloropyridine hydrochloride used can be referring to document: Organic Process Research & Development, 2010,14,562 – 567, with 2,3-lutidine is raw material, through N-oxidation, nitrated, chlorination, alcoholization, chlorination five step productive rates, can reach 65%.
the evaluated biological activity of product of the present invention:
1, the virulence test to aphid
experiment adopts spray method.First with ethanol by sample dissolution, sample is made into 5 ~ 7 series concentration with the deionized water that adds a certain amount of tensio-active agent tween 20, on the stem and leaf of Wheat of a certain amount of aphid of inoculation, evenly spray the liquid of series concentration, and do blank with clear water, every kind of concentration repeats 3 times, processing is placed in the illumination box (illumination in 12 hours, 12 hours dark) of 27 ± 1 ℃.
result checks: at 24 hours after treatment, check respectively borer population anyway.Adopt DPS statistics.
test-results: LC
50
(wheat aphid)=6.75 μ g/mL.
, control plant hopper field control effectiveness test
select one mu of certain rice area, be divided into 10Ge community, establish at random 2 as blank, remaining 8 communities are as treatment zone, before medication, investigation water rice hopper radix, selects 4 treatment zones to spray 5 % imidacloprid wettable powders after 1000 times of dilutions at random, and 5 % product of the present invention (the chloro-3-picoline of 1-(4-the methyl)-N-nitroimidazole alkane-2-base amine after 1000 times of dilutions is sprayed in other 4 treatment zones) missible oil, effectively dose is respectively 15 grams/acre, blank district spray clear water.Within after spray medicine 24 hours, check and calculate insect population decline rate and preventive effect by the borer population of living.
provado is 85% to the prevention effect of water rice hopper, product of the present invention (the chloro-3-picoline of 1-(4-methyl)-
n-nitroimidazole alkane-2-base amine) to the prevention effect of water rice hopper, be 87%.
the present invention has the following advantages:
1, chloro-3 with 4-, the chloro-3-methyl-2-of 5-dimethyl-2-chloromethylpyridine and 4-chloromethylpyridine substitutes CCMP, and raw material is easy to get, low price;
2, with sodium hydride, make acid binding agent, it ties up sour better effects if, does not need to use expensive cesium chloride to make catalyzer, and synthetic route environmental protection is with low cost;
3, the homologue that prepared compound is Provado, preparation method is simpler, and medicinal effect is good.
Embodiment
synthesizing of (the chloro-3-picoline of 4-methyl)-N-nitroimidazole alkane-2-base amine:
under room temperature, in reaction flask, 19.52 g (0.15 mol) 2-nitro imido imidazolyl alkane is dissolved with 30 mL acetonitriles, add 4.32 g (0.18 mol) sodium hydride to make acid binding agent in batches, mix, drip while stirring the 50mL acetonitrile solution of the chloro-3-methyl-2-of 17.61 g (0.1 mol) 4-chloromethylpyridine, dropwise and move to 90 ℃ of 5 h that reflux, detection reaction is complete, solvent acetonitrile is removed in underpressure distillation, residue adds the 100 mL5wt%NaOH aqueous solution, with chloroform extraction three times, organic phase merges, dry, last evaporate to dryness chloroform makes the crude product of such Provado derivative, further separate with silica gel column chromatography, make the sterling 24.89g of such Provado derivative, productive rate 92.3%.
1
H NMR (CDCl
3
, 400 MHz)
δ(ppm): 2.18 (s, 3H, C
H
3
in py), 2.84 (s, 1H,-N
H-), 3.65 (t, 1H,
H in 2-nitroaminoimidazoline), 3.82 (t, 1H,
H in 2-nitroaminoimidazoline), 4.56 (s, 2H, -C
H
2
-), 7.15 (d, J = 5.6 Hz, 1H,
H in py), 8.12 (d, J = 5.6Hz, 1H,
H in py)。
Claims (2)
1.
one kind Provado derivative, is characterized in that described class Provado derivative is: the chloro-3-picoline of 1-(4-methyl)-N-nitroimidazole alkane-2-base amine, the structural formula of described class Provado derivative is as follows:
2.
the preparation method of a kind Provado derivative described in claim 1, is characterized in that this preparation method is specific as follows:
under normal temperature, in reactor, excessive 2-nitro imido imidazolyl alkane is dissolved with acetonitrile, add sodium hydride to make acid binding agent, mix, stir the acetonitrile solution of the chloro-3-methyl-2-of the lower 4-of dropping chloromethylpyridine, dropwise rear 90 ℃ of backflow 5h, acetonitrile solvent is removed in the completely rear underpressure distillation of tlc detection reaction, then be dissolved in water, with methylene dichloride or chloroform extraction, the dry concentrated crude product that makes described class Provado derivative of organic layer, the crude product of described class Provado derivative is separated with silica gel column chromatography, make the sterling of described class Provado derivative,
the mass ratio of the chloro-3-methyl-2-of described 2-nitro imido imidazolyl alkane and 4-chloromethylpyridine is: (1.1 ~ 1.5): 1; The mass ratio of described sodium hydride and 2-nitro imido imidazolyl alkane is: (1.1 ~ 1.3): 1.
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| CN201310683741.XA CN103724324A (en) | 2013-12-13 | 2013-12-13 | Imidacloprid-like ramification and preparing method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106577728A (en) * | 2016-12-15 | 2017-04-26 | 吴娜 | Imidacloprid technical material and preparation method thereof |
| WO2019154171A1 (en) * | 2018-02-08 | 2019-08-15 | 北京颖泰嘉和生物科技股份有限公司 | Pollution-free, environmentally friendly and high-yield method for preparing imidacloprid |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742060A (en) * | 1985-02-04 | 1988-05-03 | Nihon Tokushu Noyaku Seizo K. K. | Heterocyclic compounds |
-
2013
- 2013-12-13 CN CN201310683741.XA patent/CN103724324A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4742060A (en) * | 1985-02-04 | 1988-05-03 | Nihon Tokushu Noyaku Seizo K. K. | Heterocyclic compounds |
Non-Patent Citations (1)
| Title |
|---|
| SHINZO KAGABU, ET AL: "Effect of substituents at the 5-position of the pyridine ring of imidacloprid on insecticidal activity against Periplaneta americana", 《PEST MANAGEMENT SCIENCE》, vol. 63, 31 December 2007 (2007-12-31), pages 75 - 83 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106577728A (en) * | 2016-12-15 | 2017-04-26 | 吴娜 | Imidacloprid technical material and preparation method thereof |
| WO2019154171A1 (en) * | 2018-02-08 | 2019-08-15 | 北京颖泰嘉和生物科技股份有限公司 | Pollution-free, environmentally friendly and high-yield method for preparing imidacloprid |
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Application publication date: 20140416 |