CN108822025A - A kind of preparation method of Nitenpyram - Google Patents
A kind of preparation method of Nitenpyram Download PDFInfo
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- CN108822025A CN108822025A CN201811136492.1A CN201811136492A CN108822025A CN 108822025 A CN108822025 A CN 108822025A CN 201811136492 A CN201811136492 A CN 201811136492A CN 108822025 A CN108822025 A CN 108822025A
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- China
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- preparation
- chloro
- exchange resin
- nitenpyram
- reaction
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- XHMHMQDNNPQIKW-JXMROGBWSA-N CCN(Cc(cn1)ccc1Cl)/C(/Cl)=C/[N+]([O-])=O Chemical compound CCN(Cc(cn1)ccc1Cl)/C(/Cl)=C/[N+]([O-])=O XHMHMQDNNPQIKW-JXMROGBWSA-N 0.000 description 1
- VLDUMLMCDDLHCN-UHFFFAOYSA-N CCNCc(cn1)ccc1Cl Chemical compound CCNCc(cn1)ccc1Cl VLDUMLMCDDLHCN-UHFFFAOYSA-N 0.000 description 1
- DTMCYLKNVJRMPV-JLHYYAGUSA-N CCc1ccc(CN(CC)/C(/NC)=C/[N+]([O-])=O)cn1 Chemical compound CCc1ccc(CN(CC)/C(/NC)=C/[N+]([O-])=O)cn1 DTMCYLKNVJRMPV-JLHYYAGUSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/61—Halogen atoms or nitro radicals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of Nitenpyram.This method is with the chloro- 5- pyridyl-methanamine of N- ethyl -2- and 1, the chloro- 2- nitroethylene of 1- bis- is starting material, in rudimentary chlorinated hydrocarbon solvent, acid catalyzed reaction, end of reaction, filtering removal anion exchange resin are tied up with anion exchange resin, obtain the solution of midbody compound (II), methylamine gas, end of reaction, filtering are passed through into the solution of midbody compound (II)；Filtrate concentration, crystallization, obtain target compound (I).The present invention provides a kind of reaction step is few, simple process, technique is environmentally protective, and high income, the preparation method of high-quality Nitenpyram synthesis technology.The invention is compared with prior art processes, and technological operation is easy, and operating cost is low, non-wastewater discharge, and catalyst recycling, technique is environmentally protective, good product quality, and high income is at low cost, is quite suitable for industrialized production, has extremely strong industrial application value.
Description
Technical field
The invention belongs to agricultural chemical insecticide synthesis technical fields, and in particular to a kind of preparation method of Nitenpyram.
Background technique
Nitenpyram is the nicotinic insecticide of new generation after imidacloprid, has efficient, low toxicity, interior suction, no interactions
The features such as resistance, be excellent homoptera pest pesticide control, Nitenpyram category anabasine insecticide, based on mechanism of action
Insect nerve is acted on, acetylcholine esterase inhibition activity acts on cholinergic recepter, directly stimulation parasympathetic vegetative nerve
It saves at skeletal muscle nerve neuromuscular junction, there is nerve block effect to the neuraxis synaptic receptor of insect.With good interior suction
And osmosis, low toxicity, efficiently, wide spectrum, lasting period it is longer, to crop safety without phytotoxicity the features such as, insecticidal effect due to pyridine worm,
Amidine imidacloprid equivalent type insecticide.The product is that Japanese Wu Tian company succeeded in developing in 1989.China was in 2002
Left and right just begins with relevant report and research.Nitenpyram be widely used in gardening and agriculturally prevent eliminate aphis, plant hopper, thrips, leaf
The various pests such as cicada, the pest resistant for conventional pesticides also have good activity.Nitenpyram meets the current country
The needs of outer development proposal adjustment, have preferable economic benefit and social benefit, promotion prospect is good.Therefore exploitation one
Technique is advanced, low in cost, environmentally protective synthesis technology, and the competitiveness in market can be improved, and generates very big economic benefit
And social benefit.
At present document report synthesis Nitenpyram preparation method mainly there are several types of：
Route 1：With nitromethane, carbon disulfide, dimethyl suflfate or methyl isocyanate reaction synthesis 1,1- dimethyl sulphur-based-
2- nitroethylene, it is anti-then at the chloro- 5- pyridyl-methanamine condensation of intermediate N ethyl -2- that chloro- 5 chloromethylpyridine of 2- is Material synthesis
An intermediate should be obtained, obtains Nitenpyram then at monomethyl amine aminating reaction.
This route process flow is complicated, uses that raw material sulphuric acid dimethyl ester toxicity is big, and carbon disulfide, smell is big, and operates
The disadvantages of dangerous, environmental pollution is big, at high cost is not suitable for industrialized production.
Route 2：It is reported in patent US5364989
This route uses hydrochloric acid and nitric acid nitrating, uses a large amount of acid, and waste acid treatment is difficult, and environmental protection pressure is big, condensation
Process solvent amount is big, and recycling is difficult, causes environmental pollution, and purifying products need column Image processing, reaction yield is low, cost
Height, uncomfortable industrialized production.
Summary of the invention
The purpose of the present invention is to provide a kind of technique production safeties, and easy to operate, yield is higher, and implementation cost is lower,
The preparation method of environmentally protective synthesis Nitenpyram, to solve the problem in technical background.
The present invention is a kind of preparation method of Nitenpyram, and the method comprising the steps of：
Step (a)：With the chloro- 5- pyridyl-methanamine of N- ethyl -2- and 1, the chloro- 2- nitroethylene of 1- bis- is starting material, with from
Sub-exchange resin ties up acid catalyst, and condensation reaction occurs in a solvent, and end of reaction obtains the molten of midbody compound (II)
Liquid；
Step (b)：It is passed through monomethyl amine into the solution of above-mentioned midbody compound (II), is filtered after the completion of aminating reaction,
Crystallization after filtrate decompression concentration, obtains target compound (I)-Nitenpyram；
Wherein, the preparation method of above-mentioned Nitenpyram, in step (a), the chloro- 5- pyridyl-methanamine of the N- ethyl -2- and 1,
The mol ratio that feeds intake of the chloro- 2- nitroethylene of 1- bis- is 1:1~1.2.
Wherein, the preparation method of above-mentioned Nitenpyram, in step (a), the ion exchange resin is strong basicity or weak base
Property anion exchange resin, such as can be styrene-divinylbenzene copolymer, Styrene-co-acrylamide plasma
Exchanger resin；Preferably, the ion exchange resin type number can be 201x7, D201, D301 etc..
Preferably, the dosage of the ion exchange resin is indicated with buret amount, is the chloro- 5- pyridyl-methanamine of N- ethyl -2-
Molar equivalent number 1~5 equivalent, preferably with 2~3 equivalents of the chloro- every equivalent of 5- pyridyl-methanamine of N- ethyl -2-.
Wherein, the preparation method of above-mentioned Nitenpyram, in step (a), the temperature of the condensation reaction is -10~40 DEG C.
Wherein, the preparation method of above-mentioned Nitenpyram, in step (a), the solvent is rudimentary chlorohydrocarbon, such as dichloromethane
Alkane, chloroform or 1,2, at least one of-dichloroethanes, preferably methylene chloride.
Wherein, the preparation method of above-mentioned Nitenpyram, in step (b), the monomethyl amine is monomethyl amine gas or monomethyl amine
Aqueous solution, preferably monomethyl amine gas.Preferably, the molar ratio of the monomethyl amine and the chloro- 5- pyridyl-methanamine of N- ethyl -2-
It is 1~2:1.
Wherein, the preparation method of above-mentioned Nitenpyram, in step (b), the temperature of the aminating reaction is -10~40 DEG C.
Wherein, the preparation method of above-mentioned Nitenpyram, in step (b), crystallization solvent for use be methanol, ethyl alcohol, acetone and
At least one of ethyl acetate.
Wherein, the preparation method of above-mentioned Nitenpyram, in step (b), the ion exchange resin being obtained by filtration is for recycling
It recycles.
Compared with prior art, the present invention having the advantages that：
1, the technology reaction condition is mild, and easy to operate, safety, reaction yield is high, at low cost, is suitble to industrialization big raw
It produces.
2, non-wastewater discharge, solvent are easy to recovery of applied in entire reaction process, and ion exchange resin is recyclable to be applied, technique
It is environmentally protective, it is suitble to industrial amplification production.
Specific embodiment
Further detailed description is done to technical solution of the present invention below in conjunction with specific embodiment.The following example
It is merely illustrative the ground description and interpretation present invention, and is not necessarily to be construed as limiting the scope of the invention.It is all to be based on this hair
In the range of the technology that bright above content is realized is encompassed by the present invention is directed to protect.
Unless otherwise indicated, raw materials and reagents used in the following embodiment are commercial goods, or can be by
Perception method preparation.
The preparation of 1 Nitenpyram compound (I) of embodiment
Methylene chloride 1200kg is put into 2000L reaction kettle, stirs the lower investment chloro- 5- pyridyl-methanamine of N- ethyl -2-
171kg (1kmol), 60L ion exchange resin 201x7 are cooled to Nei Wen -10 DEG C, and the chloro- 2- nitroethylene of 1,1- bis- is added dropwise
The solution of 157kg (1.1kmol) and methylene chloride 320kg are added dropwise for 3 hours, control interior 0 DEG C of temperature or less.Drop finishes, heat preservation 0
DEG C reaction 3 hours.End of reaction obtains the solution containing compound (II).This solution is continued to be cooled to Nei Wen -10 DEG C, slowly
It is passed through monomethyl amine gas 46.5kg, (1.5kmol), after controlling interior 0 DEG C of temperature hereinafter, being passed through within 3 hours calculation amount monomethyl amine gas, is protected
0 DEG C of temperature is reacted 3 hours.It finishes, filters, methylene chloride washs ion exchange resin, and filtrate is concentrated to dryness, and ethyl acetate is added
280kg, is stirred at room temperature crystallization 1 hour, is then cooled to 0 DEG C of stirring and crystallizing 3 hours, and centrifugal drying material is dried to obtain Nitenpyram
252.3kg, 99% or more purity, yield 93%.
The preparation of 2 Nitenpyram compound (I) of embodiment
Chloroform 1200kg is put into 2000L reaction kettle, stirs the lower investment chloro- 5- pyridyl-methanamine 171kg of N- ethyl -2-
(1kmol), 70L ion exchange resin D201 are cooled to 0 DEG C of interior temperature, and the chloro- 2- nitroethylene 142kg (1kmol) of 1,1- bis- is added dropwise
It with the solution of chloroform 320kg, is added dropwise within 3 hours, controls interior 10 DEG C of temperature or less.Drop finishes, and 20 DEG C of heating and heat preservation are reacted 3 hours.
End of reaction obtains the solution containing compound (II).This solution is continued to be cooled to 0 DEG C of interior temperature, is slowly introducing monomethyl amine gas
31kg (1kmol) keeps the temperature 20 DEG C and reacts 3 hours after controlling interior 10 DEG C of temperature hereinafter, being passed through within 3 hours calculation amount monomethyl amine gas.It is complete
Finish, filtering, methylene chloride washs ion exchange resin, and filtrate is concentrated to dryness, and methanol 280kg is added, it is small that crystallization 1 is stirred at room temperature
When, then it is cooled to 5 DEG C of stirring and crystallizings 3 hours, centrifugal drying material is dried to obtain Nitenpyram 246.8kg, 99% or more purity,
Yield 91%.
The preparation of 3 Nitenpyram compound (I) of embodiment
Dichloroethanes 1200kg is put into 2000L reaction kettle, stirs the lower investment chloro- 5- pyridyl-methanamine of N- ethyl -2-
171kg (1koml), 60L ion exchange resin D301 are cooled to 20 DEG C of interior temperature, and the chloro- 2- nitroethylene 170kg of 1,1- bis- is added dropwise
The solution of (1.2koml) and dichloroethanes 320kg are added dropwise for 3 hours, control interior 25 DEG C of temperature or less.Drop finishes, and is warming up to 40 DEG C
Insulation reaction 2 hours.End of reaction obtains the solution containing compound (II).This solution is continued to be cooled to 20 DEG C of interior temperature, slowly
40% monomethyl amine solution 155kg (2kmol) is instilled, controls interior 25 DEG C of temperature hereinafter, 3 hours drops finish, the 40 DEG C of insulation reactions 2 that heat up are small
When.It finishing, filters, methylene chloride washs ion exchange resin, layering, and organic phase is concentrated to dryness, ethyl alcohol 280kg is added,
Crystallization is stirred at room temperature 1 hour, is then cooled to 0 DEG C of stirring and crystallizing 3 hours, centrifugal drying material is dried to obtain Nitenpyram
241.3kg, 99% or more purity, yield 89%.
More than, embodiments of the present invention are illustrated.But the present invention is not limited to above embodiment.It is all
Within the spirit and principles in the present invention, any modification, equivalent substitution, improvement and etc. done should be included in guarantor of the invention
Within the scope of shield.
Claims (10)
1. a kind of preparation method of Nitenpyram, which is characterized in that the method comprising the steps of：
Step (a)：With the chloro- 5- pyridyl-methanamine of N- ethyl -2- and 1, the chloro- 2- nitroethylene of 1- bis- is starting material, is handed over ion
It changes resin and ties up acid catalyst, condensation reaction occurs in a solvent, end of reaction obtains the solution of midbody compound (II)；
Step (b)：It is passed through monomethyl amine into the solution of above-mentioned midbody compound (II), is filtered after the completion of aminating reaction, filtrate
Crystallization after reduced pressure obtains target compound (I)-Nitenpyram；
2. preparation method according to claim 1, which is characterized in that in step (a), the chloro- 5- pyridine of N- ethyl -2-
The mol ratio that feeds intake of methylamine and the chloro- 2- nitroethylene of 1,1- bis- is 1:1~1.2.
3. preparation method according to claim 1, which is characterized in that in step (a), the ion exchange resin is highly basic
Property or weak-base anion-exchange resin；
Preferably, the ion exchange resin is styrene-divinylbenzene copolymer, Styrene-co-acrylamide ion
Exchanger resin；
Preferably, the ion exchange resin type number is 201x7, D201, D301.
4. preparation method according to claim 1, which is characterized in that in step (a), the use of the ion exchange resin
Amount, is indicated with buret amount, is 1~5 equivalent of the molar equivalent number of the chloro- 5- pyridyl-methanamine of N- ethyl -2-, preferably with N- second
2~3 equivalents of the chloro- every equivalent of 5- pyridyl-methanamine of base -2-.
5. preparation method according to claim 1, which is characterized in that in step (a), the temperature of the condensation reaction is-
10~40 DEG C.
6. preparation method according to claim 1, which is characterized in that in step (a), the solvent is rudimentary chlorohydrocarbon,
Such as methylene chloride, chloroform or 1,2, at least one of-dichloroethanes, preferably methylene chloride.
7. preparation method according to claim 1, which is characterized in that in step (b), the monomethyl amine is monomethyl amine gas
Or monomethylamine aqueous solution, preferably monomethyl amine gas；
Preferably, the molar ratio of the monomethyl amine and the chloro- 5- pyridyl-methanamine of N- ethyl -2- is 1~2:1.
8. preparation method according to claim 1, which is characterized in that in step (b), the temperature of the aminating reaction is-
10~40 DEG C.
9. preparation method according to claim 1, which is characterized in that in step (b), crystallization solvent for use is methanol, second
At least one of alcohol, acetoneand ethyl acetate.
10. preparation method according to claim 1, which is characterized in that in step (b), the amberlite that is obtained by filtration
Rouge is used for recycling and reusing.
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| CN201811136492.1A CN108822025A (en) | 2018-09-28 | 2018-09-28 | A kind of preparation method of Nitenpyram |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121422A (en) * | 2021-04-16 | 2021-07-16 | 武威联硕生物科技有限公司 | Preparation method of nitenpyram |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5364989A (en) * | 1989-01-31 | 1994-11-15 | Takeda Chemical Industries, Ltd. | 1,1,1-trichloro-2-nitroethane production |
| CN105330593A (en) * | 2015-11-23 | 2016-02-17 | 上海晋景化学有限公司 | Improved preparation method of nitenpyram |
-
2018
- 2018-09-28 CN CN201811136492.1A patent/CN108822025A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5364989A (en) * | 1989-01-31 | 1994-11-15 | Takeda Chemical Industries, Ltd. | 1,1,1-trichloro-2-nitroethane production |
| CN105330593A (en) * | 2015-11-23 | 2016-02-17 | 上海晋景化学有限公司 | Improved preparation method of nitenpyram |
Non-Patent Citations (1)
| Title |
|---|
| 贡长生 张克立 主编: "《新型功能材料》", 31 January 2001, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113121422A (en) * | 2021-04-16 | 2021-07-16 | 武威联硕生物科技有限公司 | Preparation method of nitenpyram |
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Application publication date: 20181116 |