CN110483382A - A kind of green synthesis method of 2-vhloro-5-chloromethylpyridine - Google Patents
A kind of green synthesis method of 2-vhloro-5-chloromethylpyridine Download PDFInfo
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- CN110483382A CN110483382A CN201910879716.6A CN201910879716A CN110483382A CN 110483382 A CN110483382 A CN 110483382A CN 201910879716 A CN201910879716 A CN 201910879716A CN 110483382 A CN110483382 A CN 110483382A
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- vhloro
- chloromethylpyridine
- synthesis method
- phosgene
- green synthesis
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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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- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of green synthesis methods of 2-vhloro-5-chloromethylpyridine, by CCC (the chloro- 2 chloromethyl -1- aldehyde valeronitrile of 2-) and DMF (N, dinethylformamide) it is dissolved in solvent, it is passed through phosgene and carries out cyclization reaction, after reaction, with the unreacted phosgene of nitrogen stripping, through precipitation, it is product 2-vhloro-5-chloromethylpyridine that vacuum distillation, which obtains brown liquid,.Using synthetic method of the invention, no effuent discharge may be implemented, reduce production cost, and synthesis technology is simple, product yield high.
Description
Technical field
The present invention relates to technical field of organic chemistry more particularly to a kind of green syt sides of 2-vhloro-5-chloromethylpyridine
Method.
Background technique
2-vhloro-5-chloromethylpyridine is the key intermediate of Novel high-efficient pesticide imidacloprid, and this kind of pesticide molecules
In most insecticidal activity structure division.The process route reported at present is mainly cyclopentadiene route, wherein main when cyclization
It is with phosphorus oxychloride is cyclizing agent, reaction terminates to need to hydrolyze phosphorus oxychloride, causes containing a large amount of phosphoric acid in technique waste water, right
Environment pollutes, while enterprise is that processing phosphoric acid waste water increases production cost.For this purpose, to provide a kind of 2- chloro- by the present invention
The green synthesis method of 5- chloromethylpyridine fundamentally solves the problems, such as phosphoric acid waste water.
Summary of the invention
It is an object of the invention to: a kind of green synthesis method of 2-vhloro-5-chloromethylpyridine is provided, zero waste water is realized
Discharge, reduces production cost, synthesis technology is simple, product yield high.
The technical solution adopted by the invention is as follows:
To achieve the above object, the present invention provides a kind of green synthesis method of 2-vhloro-5-chloromethylpyridine, by CCC (2-
Chloro- 2 chloromethyl -1- aldehyde valeronitrile) and DMF (n,N-Dimethylformamide) be dissolved in solvent, be passed through phosgene carry out cyclization reaction, instead
After answering, with the unreacted phosgene of nitrogen stripping, through precipitation, it is the chloro- 5- chloromethane of product 2- that vacuum distillation, which obtains brown liquid,
Yl pyridines.
Reaction equation are as follows:
Preferably, the molar ratio of the CCC and phosgene is 1:(1.05~1.3).
Preferably, the weight ratio of the solvent, DMF and CCC are 1:(0.4~0.6): (0.9~1.5).
Preferably, the solvent is toluene, chlorobenzene, hexamethylene, dichloroethanes, any one in chloroform.
Preferably, the cyclization reaction temperature is 20~95 DEG C.
Preferably, the nitrogen stripping phosgene time is 2~3 hours.
In conclusion by adopting the above-described technical solution, the beneficial effects of the present invention are:
1. the present invention is cyclizing agent using phosgene, it is passed directly into reaction solution, after reaction, is returned with nitrogen stripping
Unreacted phosgene is received, does not need to add water processing solution, absolutely not waste water generates, and realizes no effuent discharge.
2. the present invention recycles unreacted phosgene using stripping, eliminates and be quenched, neutralize and extract, simplify technique
Process, operation is simpler, reduces production cost.
3. the present invention is cyclizing agent using phosgene, the reaction time is short, product yield high.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with the embodiment of the present invention, it is clear that retouched
The embodiment stated is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, originally
Field those of ordinary skill every other embodiment obtained without making creative work, belongs to the present invention
The range of protection.
Embodiment 1
CCC0.1mol and DMF0.05mol are dissolved in the toluene of 0.11mol, 0.11mol phosgene is passed through at 20 DEG C, is kept
Temperature is passed through 2 hours, then uses the unreacted phosgene of nitrogen stripping 2 hours, precipitation is evaporated under reduced pressure to 14.9 grams of palm fibres at 30 DEG C
Color liquid, GC quantitative detection contain dichloro 99.2%, yield 91.2%.
Embodiment 2
CCC0.1mol and DMF0.05mol are dissolved in the toluene of 0.11mol, 0.12mol phosgene is passed through at 20 DEG C, is kept
Temperature is passed through 3 hours, then uses the unreacted phosgene of nitrogen stripping 2 hours, precipitation at 40 DEG C, is evaporated under reduced pressure to 15.9 grams admittedly
Body, GC quantitative detection contain dichloro 89.2%, yield 88.0%.
Embodiment 3
CCC0.1mol and DMF0.06mol are dissolved in the toluene of 0.11mol, 0.13 moles of phosgene is passed through at 20 DEG C, is protected
Temperature is held at 60 DEG C, is passed through 5 hours, then uses the unreacted phosgene of nitrogen stripping 3 hours, precipitation is evaporated under reduced pressure to 14.9 grams
Brown liquid, GC quantitative detection contain dichloro 99.2%, yield 91.2%.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify to technical solution documented by previous embodiment, or some or all of the technical features are equal
Replacement；And these are modified or replaceed, the model for technical solution of the embodiment of the present invention that it does not separate the essence of the corresponding technical solution
It encloses, should all cover within the scope of the claims and the description of the invention.
Claims (6)
1. a kind of green synthesis method of 2-vhloro-5-chloromethylpyridine, which is characterized in that CCC and DMF are dissolved in solvent, led to
Enter phosgene and carry out cyclization reaction, after reaction, with the unreacted phosgene of nitrogen stripping, through precipitation, vacuum distillation obtains brown
Liquid is product 2-vhloro-5-chloromethylpyridine.
2. a kind of green synthesis method of 2-vhloro-5-chloromethylpyridine according to claim 1, which is characterized in that described
The molar ratio of CCC and phosgene is 1:(1.05~1.3).
3. a kind of green synthesis method of 2-vhloro-5-chloromethylpyridine according to claim 1, which is characterized in that described
The weight ratio of solvent, DMF and CCC are 1:(0.4~0.6): (0.9~1.5).
4. a kind of green synthesis method of 2-vhloro-5-chloromethylpyridine according to claim 3, which is characterized in that described
Solvent is toluene, chlorobenzene, hexamethylene, dichloroethanes, any one in chloroform.
5. a kind of green synthesis method of 2-vhloro-5-chloromethylpyridine according to claim 1, which is characterized in that described
Cyclization reaction temperature is 20~95 DEG C.
6. a kind of green synthesis method of 2-vhloro-5-chloromethylpyridine according to claim 1, which is characterized in that described
The nitrogen stripping phosgene time is 2~3 hours.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910879716.6A CN110483382A (en) | 2019-09-18 | 2019-09-18 | A kind of green synthesis method of 2-vhloro-5-chloromethylpyridine |
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| CN201910879716.6A CN110483382A (en) | 2019-09-18 | 2019-09-18 | A kind of green synthesis method of 2-vhloro-5-chloromethylpyridine |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287347A (en) * | 1980-05-12 | 1981-09-01 | Ciba-Geigy Corporation | Process for producing 2,3,5-trichloropyridine |
| CN101948424A (en) * | 2010-09-30 | 2011-01-19 | 南开大学 | Preparation method for 2-chloro-5-chloromethyl pyridine |
| CN102285913A (en) * | 2010-06-18 | 2011-12-21 | 北京英力精化技术发展有限公司 | Synthesis method of CMP (2-chloro-5-methylpyridine) |
| CN105837499A (en) * | 2016-03-31 | 2016-08-10 | 常州大学 | Synthetic method for 2,3-chloro-5-chloromethylpyridine |
| CN106699646A (en) * | 2016-11-12 | 2017-05-24 | 江苏长青生物科技有限公司 | Synthetic method of acetamiprid |
-
2019
- 2019-09-18 CN CN201910879716.6A patent/CN110483382A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287347A (en) * | 1980-05-12 | 1981-09-01 | Ciba-Geigy Corporation | Process for producing 2,3,5-trichloropyridine |
| CN102285913A (en) * | 2010-06-18 | 2011-12-21 | 北京英力精化技术发展有限公司 | Synthesis method of CMP (2-chloro-5-methylpyridine) |
| CN101948424A (en) * | 2010-09-30 | 2011-01-19 | 南开大学 | Preparation method for 2-chloro-5-chloromethyl pyridine |
| CN105837499A (en) * | 2016-03-31 | 2016-08-10 | 常州大学 | Synthetic method for 2,3-chloro-5-chloromethylpyridine |
| CN106699646A (en) * | 2016-11-12 | 2017-05-24 | 江苏长青生物科技有限公司 | Synthetic method of acetamiprid |
Non-Patent Citations (3)
| Title |
|---|
| 张梅等: "新法制备2-氯-5-氯甲基吡啶", 《农药》 * |
| 杜友兴等: "2-氯-5-氯甲基吡啶的合成研究", 《精细石油化工进展》 * |
| 陈兆麟等: "《光气安全评价与管理》", 30 June 2011, 华东理工大学出版社 * |
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Application publication date: 20191122 |