CN106187868A - A kind of preparation method of Acetamiprid - Google Patents
A kind of preparation method of Acetamiprid Download PDFInfo
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- CN106187868A CN106187868A CN201610556702.7A CN201610556702A CN106187868A CN 106187868 A CN106187868 A CN 106187868A CN 201610556702 A CN201610556702 A CN 201610556702A CN 106187868 A CN106187868 A CN 106187868A
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- acetamiprid
- methylamine
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- 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
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Abstract
The present invention relates to the preparation method of a kind of Acetamiprid, described preparation method is synthesized N (6 chlorine 3 picolyl) methylamine by 2 chlorine 5 chloromethylpyridine and methylamine water solution, cyanaoethyl methacrylate is synthesized by acetonitrile, ethanol and cyanamide, then is synthesized Acetamiprid further by N (6 chlorine 3 picolyl) methylamine and cyanaoethyl methacrylate.It is an advantage of the current invention that: the preparation method of Acetamiprid of the present invention, by controlling reaction condition so that the feed stock conversion of use improves, it is adaptable to commercial production；Additionally, the Acetamiprid product purity being prepared into by this preparation method is high, impurity content is few, molar yield is high, achieves good economic benefit.
Description
Technical field
The invention belongs to chemical field, particularly to the preparation method of a kind of Acetamiprid.
Background technology
Acetamiprid is chlorination nicotine compound, is a kind of novel pesticide, belongs to Nitromethylene heterocycle compound, makees
For the nAChR of insect nerve system synapses, interference insect is neural stimulates conduction, causes god
Through system, a passage is blocked up, causes neurotransmitter acetylcholine in the accumulation of synapses, thus causes insect paralysis, the most extremely
Die.Have tag, poison stomach effect, have stronger osmosis, quick-acting number simultaneously, the lasting period is long.
Finding through retrieval, patent CN 104803910 A proposes the production technology of Acetamiprid, comprises the following steps: (1)
Amination: at room temperature, joins in aminating reaction still by chloroform, starts to be passed through monomethyl amine gas under insertion liquid in chloroformic solution
Body, and under this temperature, normal pressure drips 2-vhloro-5-chloromethylpyridine in reactor, makes reaction temperature be less than 20 DEG C, material is cold
But to room temperature, adding water stirring 1-2h, stratification, Distillation recovery chloroform under normal pressure, after the material after precipitation is cooled to room temperature
Add ethanol to dissolve, and proceed to next step reaction；(2) condensation: at room temperature, the ethanol solution of aminate, cyanaoethyl methacrylate are pressed
Ratio puts into opens stirring in condensation kettle, logical chilled brine cools to 0 DEG C of crystallization, has white solid to separate out, refilter, and is dried,
Filtrate send ethanol distillation still at 78-80 DEG C, Distillation recovery ethanol under condition of normal pressure.Aminating reaction temperature of the present invention is relatively low, by-product
Thing is few, and waste water is few, and condensation reaction is simple, and the response time is short, energy efficient, and separately this reaction is anhydrous response, does not produce waste water；But
Have the disadvantage in that the conversion ratio of 1. use raw materials is low；2. product purity is relatively low.
Therefore, the preparation side of a kind of Acetamiprid that can improve feed stock conversion, product purity and minimizing wastewater flow rate is researched and developed
Method is necessary.
Summary of the invention
The technical problem to be solved in the present invention is to provide one and can improve feed stock conversion, product purity and reduce waste water
The preparation method of the Acetamiprid of amount.
For solving above-mentioned technical problem, the technical scheme is that the preparation method of a kind of Acetamiprid, its innovative point exists
In: described preparation method is synthesized N-(6-chloro-3-pyridylmethyl by 2-vhloro-5-chloromethylpyridine and methylamine water solution) first
Amine, is synthesized cyanaoethyl methacrylate by acetonitrile, ethanol and cyanamide, then by N-(6-chloro-3-pyridylmethyl) methylamine and cyanaoethyl methacrylate
Synthesize Acetamiprid further.
Further, the specifically comprising the following steps that of described preparation method
(1) in reactor A, add 2-vhloro-5-chloromethylpyridine, be then slowly added dropwise the methylamine that mass concentration is 40% water-soluble
Liquid, controlling time for adding is 1～1.5h, and stirring is warming up to 60～65 DEG C, insulation reaction 5～6h, and after reaction terminates, decompression is de-
Water obtains N-(6-chloro-3-pyridylmethyl) methylamine；
(2) in reactor B, add acetonitrile, ethanol and solvent toluene, and be cooled to 3～5 DEG C, under this temperature conditions, be passed through chlorine
Changing hydrogen, ventilate 9～10h, after ventilation terminates, adding mass percent concentration is 28% to be that cyanamide aqueous solution is at 3～5 DEG C
Insulation reaction 1～3h, after reaction terminates, with between the liquid caustic soda regulation PH to 6.0～6.5 that mass percent mass concentration is 30%, surely
In 10～15 DEG C of insulation reaction 1～2h after Ding, then wash with saturated brine, take oil reservoir rectification and obtain cyanaoethyl methacrylate；
(3) in reactor C, the N-(6-chloro-3-pyridylmethyl in ethanol and step (1) is added) methylamine, add step (2)
In cyanaoethyl methacrylate, be then heated to 60～65 DEG C, and insulation reaction 6～7 hours, reaction terminates, and is cooled to 0～5 DEG C,
Stratification again, filters, and washs with saturated aqueous common salt, after drying, obtains Acetamiprid.
Further, in described step (1), the mol ratio of 2-vhloro-5-chloromethylpyridine and methylamine water solution is 1:1.2.
Further, in described step (2), acetonitrile, ethanol, hydrogen chloride are 1:1.05:1.05 with the mol ratio of cyanamide:
1.05。
Further, N-(6-chloro-3-pyridylmethyl in described step (3)) methylamine with the mol ratio of cyanaoethyl methacrylate is
1.05:1。
It is an advantage of the current invention that: the preparation method of Acetamiprid of the present invention, by controlling reaction condition so that use former
Material conversion ratio improves, and preparation method safety, it is adaptable to commercial production；Additionally, the Acetamiprid being prepared into by this preparation method
Product purity is high, impurity content is few, molar yield is high, achieves good economic benefit.
Detailed description of the invention
The following examples can make professional and technical personnel that the present invention is more fully understood, but the most therefore by this
Bright it is limited among described scope of embodiments.
Embodiment 1
N-(6-chloro-3-pyridylmethyl) preparation of methylamine:
In 500ml four-hole boiling flask, add 162g 2-vhloro-5-chloromethylpyridine, 250ml constant pressure funnel adds 93g
Mass percentage concentration is to be slowly added dropwise methylamine under 40% methylamine water solution, stirring state；60 DEG C of reactions it are warming up to after dropping,
After insulation reaction 6h, after the distillation dehydration that reduced pressure by material, obtain 157g N-(6-chloro-3-pyridylmethyl) methylamine, purity 95.8%,
Yield 95.6%.
Embodiment 2
The preparation of cyanaoethyl methacrylate:
Being sequentially added into 41g acetonitrile, 42g ethanol and 100g solvent toluene in 500ml four-hole boiling flask, temperature is down to 3-5 DEG C, at this
It is passed through hydrogen chloride gas 38g under temperature conditions, after ventilation in about 10 hours terminates, adds cyanamide aqueous solution insulation reaction, reaction
After end, with between liquid caustic soda regulation PH to 6.0-6.5, stablize the reaction in a hour of follow-up continuous insulation reaction and terminate.Use saturated brine again
Washing, takes oil reservoir rectification and obtains 96.8g cyanaoethyl methacrylate.Yield 85.6%, content 99%.
Embodiment 3
The preparation of Acetamiprid:
157.5gN-(6-chloro-3-pyridylmethyl is added in 500ml) methylamine and 100g ethanol, add 112g cyanaoethyl methacrylate,
Being heated to 65 DEG C, insulation reaction 6～7 hours, reaction terminates, and is cooled to 0 DEG C, stratification, filters, washes by saturated salt
Wash, after drying, obtain Acetamiprid 22.1g, purity 96.8%, yield 96.6%.
In the present embodiment, Acetamiprid product analyzes that to obtain content be 96.8% after testing, and reaction yield is 72.5%.
The ultimate principle of the present invention and principal character and advantages of the present invention have more than been shown and described.The skill of the industry
The art personnel simply explanation it should be appreciated that the present invention is not restricted to the described embodiments, described in above-described embodiment and description
The principle of the present invention, without departing from the spirit and scope of the present invention, the present invention also has various changes and modifications, these
Changes and improvements both fall within scope of the claimed invention.Claimed scope by appending claims and
Its equivalent defines.
Claims (5)
1. the preparation method of an Acetamiprid, it is characterised in that: described preparation method is by 2-vhloro-5-chloromethylpyridine and methylamine water
Solution reaction synthesis N-(6-chloro-3-pyridylmethyl) methylamine, acetonitrile, ethanol and cyanamide cyanaoethyl methacrylate it is synthesized, then by
N-(6-chloro-3-pyridylmethyl) methylamine and cyanaoethyl methacrylate synthesize Acetamiprid further.
The preparation method of Acetamiprid the most according to claim 1, it is characterised in that: the concrete steps of described preparation method are such as
Under:
(1) in reactor A, add 2-vhloro-5-chloromethylpyridine, be then slowly added dropwise the methylamine that mass concentration is 40% water-soluble
Liquid, controlling time for adding is 1～1.5h, and stirring is warming up to 60～65 DEG C, insulation reaction 5～6h, and after reaction terminates, decompression is de-
Water obtains N-(6-chloro-3-pyridylmethyl) methylamine；
(2) in reactor B, add acetonitrile, ethanol and solvent toluene, and be cooled to 3～5 DEG C, under this temperature conditions, be passed through chlorine
Changing hydrogen, ventilate 9～10h, after ventilation terminates, adding mass percent concentration is 28% to be that cyanamide aqueous solution is at 3～5 DEG C
Insulation reaction 1～3h, after reaction terminates, with between the liquid caustic soda regulation PH to 6.0～6.5 that mass percent mass concentration is 30%, surely
In 10～15 DEG C of insulation reaction 1～2h after Ding, then wash with saturated brine, take oil reservoir rectification and obtain cyanaoethyl methacrylate；
(3) in reactor C, the N-(6-chloro-3-pyridylmethyl in ethanol and step (1) is added) methylamine, add step (2)
In cyanaoethyl methacrylate, be then heated to 60～65 DEG C, and insulation reaction 6～7 hours, reaction terminates, and is cooled to 0～5 DEG C,
Stratification again, filters, and washs with saturated aqueous common salt, after drying, obtains Acetamiprid.
The preparation method of Acetamiprid the most according to claim 2, it is characterised in that: 2-chloro-5-chloromethane in described step (1)
Yl pyridines is 1:1.2 with the mol ratio of methylamine water solution.
The preparation method of Acetamiprid the most according to claim 2, it is characterised in that: acetonitrile in described step (2), ethanol,
Hydrogen chloride is 1:1.05:1.05:1.05 with the mol ratio of cyanamide.
The preparation method of Acetamiprid the most according to claim 2, it is characterised in that: the chloro-3-of N-(6-in described step (3)
Picolyl) mol ratio of methylamine and cyanaoethyl methacrylate is 1.05:1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610556702.7A CN106187868A (en) | 2016-07-15 | 2016-07-15 | A kind of preparation method of Acetamiprid |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501172A (en) * | 2017-09-03 | 2017-12-22 | 江苏长青农化股份有限公司 | The production technology of Acetamiprid |
| CN110256295A (en) * | 2019-07-03 | 2019-09-20 | 宁夏贝利特生物科技有限公司 | The synthetic method of N- cyan ethyl ethylimidoote |
| CN111808018A (en) * | 2020-08-14 | 2020-10-23 | 青岛恒宁生物科技有限公司 | Production process of acetamiprid |
| KR20210022320A (en) | 2019-08-20 | 2021-03-03 | 주식회사 엘지화학 | Method for purifying 1-(6-chlolopyridine-3-yl)-n-methylmethanamine |
| CN114605319A (en) * | 2020-12-09 | 2022-06-10 | 南通天泽化工有限公司 | Preparation method of acetamiprid |
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| CN102174013A (en) * | 2011-03-10 | 2011-09-07 | 江苏长青农化股份有限公司 | New synthesis technology of acetamiprid |
| CN102942505A (en) * | 2012-10-31 | 2013-02-27 | 甘肃省化工研究院 | Synthetic method of N-cyan ethyl ethylimidoote |
| CN104803910A (en) * | 2015-03-26 | 2015-07-29 | 江苏长青农化南通有限公司 | Production process of acetamiprid |
| CN105152976A (en) * | 2015-07-28 | 2015-12-16 | 南通天泽化工有限公司 | Improved process of ethyl N-cyanoethanimideate preparation method |
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| CN102174013A (en) * | 2011-03-10 | 2011-09-07 | 江苏长青农化股份有限公司 | New synthesis technology of acetamiprid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107501172A (en) * | 2017-09-03 | 2017-12-22 | 江苏长青农化股份有限公司 | The production technology of Acetamiprid |
| CN110256295A (en) * | 2019-07-03 | 2019-09-20 | 宁夏贝利特生物科技有限公司 | The synthetic method of N- cyan ethyl ethylimidoote |
| KR20210022320A (en) | 2019-08-20 | 2021-03-03 | 주식회사 엘지화학 | Method for purifying 1-(6-chlolopyridine-3-yl)-n-methylmethanamine |
| CN111808018A (en) * | 2020-08-14 | 2020-10-23 | 青岛恒宁生物科技有限公司 | Production process of acetamiprid |
| CN111808018B (en) * | 2020-08-14 | 2022-06-14 | 青岛恒宁生物科技有限公司 | Production process of acetamiprid |
| CN114605319A (en) * | 2020-12-09 | 2022-06-10 | 南通天泽化工有限公司 | Preparation method of acetamiprid |
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Application publication date: 20161207 |