CN104610136B - A kind of synthetic method of the trichloromethyl pyridine of 2 chlorine 5 - Google Patents
A kind of synthetic method of the trichloromethyl pyridine of 2 chlorine 5 Download PDFInfo
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- CN104610136B CN104610136B CN201410060990.8A CN201410060990A CN104610136B CN 104610136 B CN104610136 B CN 104610136B CN 201410060990 A CN201410060990 A CN 201410060990A CN 104610136 B CN104610136 B CN 104610136B
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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 invention discloses a kind of synthetic method of the PMC of 2 chlorine 5.Organic solvent, acidic buffer agent solution and initiator are added in 3 picolines, regulation solution ph is 45；Nitrogen is passed through, stirring is warming up to 80 100 DEG C, stops logical nitrogen and be passed through chlorine, continue temperature reaction；Stop heating, close chlorine sampling valve, be passed through nitrogen, bubbling is caught up with after chlorine, reaction solution vacuum distillation precipitation, obtains brownish red oily liquids, finally purification obtains finished product.The present invention uses liquid phase chlorination method, raw material is reacted in the liquid state, while adding acidic buffer agent solution and regulation pH value 45, reduces the generation of accessory substance, the yield of target product is reached 90% or so.
Description
Technical field
The present invention relates to a kind of synthetic method of 2- chloro-5-trichloromethylpyridines, belong to organic chemical synthesis field.
Background technology
2-vhloro-5-chloromethylpyridine (abbreviation CCMP) is the anabasine pesticides such as pesticide imidacloprid, Acetamiprid, paichongding
Important intermediate, available for preparing pharmaceuticals, agricultural chemicals and biological agent etc., particularly synthesizing efficient novel agrochemical pyrrole fluorine
The spirit of chlorine standing grain, imidacloprid and the vital intermediate of following novel pesticide containing chloropyridines, are closed with 2- chloro-5-trichloromethylpyridines
Into new varieties of pesticides containing chloropyridines, development and exploitation energetically is at home and abroad just being obtained at present.
Mainly there are three using the route of cyclization method synthesis 2-vhloro-5-chloromethylpyridine at present, be benzylamine method, ring penta respectively
Diene method, morpholine method.
In the chlorination reaction of benzylamine method and morpholine method, there is chlorination inequality, easily form many chloro accessory substances, separation is tired
Difficulty, product purity is not ideal enough.
In cyclopentadiene method, ring-closure reaction generation 2-vhloro-5-chloromethylpyridine, it is to avoid many chlorine produced during chloro
For accessory substance, product purity is higher, is the route that domestic most producers select.But the chloro of cyclopentadiene method and cyclization process
Need to use a large amount of DMFs, and without effective recovery method, while producing a large amount of waste water, brought sternly to environment
Ghost image rings.
The preparation method of 2- chloro-5-trichloromethylpyridines is disclosed in the A of Chinese patent CN 102452977, using 3- first
Yl pyridines are raw material, under conditions of organic solvent and chlorine are present, trigger through initiator, react and close through a step liquid phase chlorination method
Into 2- chloro-5-trichloromethylpyridines, and purify obtaining finished product.The chloro- 5- trichloromethyls pyrroles of 2- obtained in the synthetic route
Pyridine accessory substance is high, and yield can only achieve 80% or so.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of 2- chloro-5-trichloromethylpyridines.
The technical solution for realizing the object of the invention is：A kind of synthetic method of 2- chloro-5-trichloromethylpyridines, including
Following steps：Organic solvent, acidic buffer agent solution and initiator are added in 3- picolines, regulation solution ph is in 4-5；
Nitrogen is passed through, stirring is warming up to 80-100 DEG C, stops logical nitrogen and be passed through chlorine, continue temperature reaction；Stop heating, close chlorine
Gas sampling valve, is passed through nitrogen, and bubbling is caught up with after chlorine, reaction solution vacuum distillation precipitation, obtains brownish red oily liquids, finally purify
To finished product.
In above-mentioned steps, described organic solvent is nitrobenzene.
In above-mentioned steps, described acidic buffer agent solution is sodium dihydrogen phosphate.
In above-mentioned steps, described initiator is phosphorus trichloride.
In above-mentioned steps, the addition total amount of described initiator is the 2%-5% of 3- picoline quality.
In above-mentioned steps, the addition of described organic solvent is 3-4 times of 3- picoline quality.
In above-mentioned steps, the addition of described buffer agent solution is 1-2 times of organic solvent volume.
In above-mentioned steps, described reaction temperature is 120-160 DEG C, reaction time 12-20h.
Compared with prior art, the advantage of the invention is that：Using liquid phase chlorination method, raw material is set to carry out in the liquid state instead
Should, while adding acidic buffer agent solution and regulation pH value in 4-5, the generation of accessory substance is reduced, makes the yield of target product
Reach 90% or so.
Embodiment
Embodiment 1
10g 3- picolines, 30mL nitrobenzene and 45ml buffer agent solutions are added in four-hole boiling flask, using watery hydrochloric acid
Solution ph is adjusted 4 or so, while adding 0.2g phosphorus trichlorides.Nitrogen is passed through, electromagnetic agitation is warming up to 80 DEG C, stops logical
Nitrogen simultaneously switches and is passed through chlorine, is continuously heating to 120 DEG C, under constant temperature, chlorine blistering reaction 12h stops heating, closes chlorine and enter
Sample valve, is passed through nitrogen, and bubbling catches up with chlorine 1h.After reaction solution vacuum distillation precipitation, brownish red oily liquids is obtained.High-vacuum fractionation is carried
Pure products, collect distillate.After chloroform extraction, combining extraction liquid depressurizes after precipitation, obtains the faint yellow oilies of 18.9g
Liquid, the yield of product 2- chloro-5-trichloromethylpyridines is 89.6%.
Embodiment 2
10g 3- picolines, 25mL nitrobenzene and 25ml buffer agent solutions are added in four-hole boiling flask, using watery hydrochloric acid
Solution ph is adjusted 4.5 or so, while adding 0.3g phosphorus trichlorides.Nitrogen is passed through, electromagnetic agitation is warming up to 100 DEG C, stopping
Lead to nitrogen and switch and be passed through chlorine, be continuously heating to 140 DEG C, under constant temperature, chlorine blistering reaction 16h stops heating, closes chlorine
Sampling valve, is passed through nitrogen, and bubbling catches up with chlorine 1h.After reaction solution vacuum distillation precipitation, brownish red oily liquids is obtained.High-vacuum fractionation
Purified product, collects distillate.After chloroform extraction, combining extraction liquid depressurizes after precipitation, obtains the faint yellow oil of 19.4g
Shape liquid, the yield of product 2- chloro-5-trichloromethylpyridines is 91.3%.
Embodiment 3
10g 3- picolines, 45mL nitrobenzene and 90ml buffer agent solutions are added in four-hole boiling flask, using watery hydrochloric acid
Solution ph is adjusted 5 or so, while adding 0.5g phosphorus trichlorides.Nitrogen is passed through, electromagnetic agitation is warming up to 90 DEG C, stops logical
Nitrogen simultaneously switches and is passed through chlorine, is continuously heating to 160 DEG C, under constant temperature, chlorine blistering reaction 20h stops heating, closes chlorine and enter
Sample valve, is passed through nitrogen, and bubbling catches up with chlorine 1h.After reaction solution vacuum distillation precipitation, brownish red oily liquids is obtained.High-vacuum fractionation is carried
Pure products, collect distillate.After chloroform extraction, combining extraction liquid depressurizes after precipitation, obtains the faint yellow oilies of 19.1g
Liquid, the yield of product 2- chloro-5-trichloromethylpyridines is 90.4%.
Claims (1)
1. a kind of synthetic method of the chloro- 5- trichloromethyl pyridines of 2-, it is characterised in that comprise the following steps：In 3- methyl pyrroles
Organic solvent, acidic buffer agent solution and initiator are added in pyridine, regulation solution ph is in 4-5；Nitrogen is passed through, stirring is warming up to
80-100 DEG C, stop logical nitrogen and be passed through chlorine, continue temperature reaction；Stop heating, close chlorine sampling valve, be passed through nitrogen,
Bubbling is caught up with after chlorine, reaction solution vacuum distillation precipitation, obtains brownish red oily liquids, and finally purification obtains finished product；
Described organic solvent is nitrobenzene, and the addition of organic solvent is 3-4 times of 3- picoline quality；
Described acidic buffer agent solution is sodium dihydrogen phosphate, and the addition of acidic buffer agent solution is organic solvent volume
1-2 times；
Described initiator is phosphorus trichloride, and the addition total amount of initiator is the 2%-5% of 3- picoline quality；
Described reaction temperature is 120-160 DEG C, reaction time 12-20h.
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| CN201410060990.8A CN104610136B (en) | 2014-02-21 | 2014-02-21 | A kind of synthetic method of the trichloromethyl pyridine of 2 chlorine 5 |
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| CN201410060990.8A CN104610136B (en) | 2014-02-21 | 2014-02-21 | A kind of synthetic method of the trichloromethyl pyridine of 2 chlorine 5 |
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| CN104610136B true CN104610136B (en) | 2017-07-14 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106397308A (en) * | 2015-07-28 | 2017-02-15 | 江苏吉华化工有限公司 | Process for preparing 2-chloro-5-chloromethylpyridine from trimethylpyridine-phosphamide |
| CN106380445A (en) * | 2015-07-28 | 2017-02-08 | 江苏吉华化工有限公司 | Method for preparing 2-chloro-5-chloromethylpyridine from 2-methylpyridine |
| CN106187869A (en) * | 2016-07-28 | 2016-12-07 | 南京红太阳生物化学有限责任公司 | A kind of method of synthesis 2 chlorine 5 chloromethylpyridine |
| CN107162962A (en) * | 2017-05-12 | 2017-09-15 | 江苏克胜作物科技有限公司 | The control method of the PMC dimer of 2 chlorine 5 |
| CN107628989B (en) * | 2017-10-26 | 2020-07-24 | 南京红太阳生物化学有限责任公司 | Synthetic method of 2-chloro-5-chloromethylpyridine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342648A (en) * | 2000-09-13 | 2002-04-03 | 中国科学院大连化学物理研究所 | Process for synthesizing 2-Cl-5-trifluoromethyl pyridine |
| CN102452977A (en) * | 2010-10-28 | 2012-05-16 | 宁波大学 | Method for preparing 2-chloro-5-trichloromethylpyridine |
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| DE4016175A1 (en) * | 1990-05-19 | 1991-11-21 | Bayer Ag | SIDE CHAIN CHLORINE OF ALKYLATED NITROGEN HETEROAROMATS |
| CN1631881A (en) * | 2003-12-22 | 2005-06-29 | 中国科学院大连化学物理研究所 | Process for synthesizing 2-chloro-5-chloromethylpyridine |
| CN1966494B (en) * | 2006-10-19 | 2010-05-26 | 沙隆达集团公司 | 2-chloro-5-chloromethyl pyridine refining method |
| CN102942518B (en) * | 2012-11-30 | 2014-06-04 | 江苏优嘉化学有限公司 | Chlorination synthesis method of pyridine derivatives |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342648A (en) * | 2000-09-13 | 2002-04-03 | 中国科学院大连化学物理研究所 | Process for synthesizing 2-Cl-5-trifluoromethyl pyridine |
| CN102452977A (en) * | 2010-10-28 | 2012-05-16 | 宁波大学 | Method for preparing 2-chloro-5-trichloromethylpyridine |
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