CN106187871A - A kind of method preparing 3,5,6 trichloropyridine 2 sodium alkoxide - Google Patents
A kind of method preparing 3,5,6 trichloropyridine 2 sodium alkoxide Download PDFInfo
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- CN106187871A CN106187871A CN201610524597.9A CN201610524597A CN106187871A CN 106187871 A CN106187871 A CN 106187871A CN 201610524597 A CN201610524597 A CN 201610524597A CN 106187871 A CN106187871 A CN 106187871A
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- trichloropyridine
- chloride
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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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/63—One oxygen atom
- C07D213/64—One oxygen atom attached in position 2 or 6
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- Pyridine Compounds (AREA)
Abstract
The invention discloses one and prepare 3, the method for 5,6 trichloropyridine 2 sodium alkoxide, raw material trichloro-acetic chloride and acrylonitrile are put in mixed solvent, at CuCl2In the presence of catalyst A, heat temperature raising carries out back flow reaction, after backflow terminates, and the liquid caustic soda added in reactor, regulation pH, carries out aromatization, fully filters after reaction, crude product is put into equipped with water, catalyst B, alkali reactor in, temperature rising reflux, then sucking filtration, be dried, obtain finished product.The inventive method uses " one kettle way " to react; and without desolvation in subsequent handling, it is substantially reduced cost and the energy consumption of raw materials technology, beneficially large-scale production; and avoid the method for fractional steps is passed through the HCl corrosion to equipment and the injury of human body, reduce equipment cost；Technique synthetic operation is simple, and the response time shortens half, and wastewater flow rate is reduced to 1/2, energy-saving and emission-reduction, environmental protection.
Description
Technical field
The present invention relates to field of fine chemical, specifically one prepares 3, the method for 5,6-trichloropyridine-2-sodium alkoxide.
Background technology
3,5,6-trichloropyridine-2-sodium alkoxide, molecular formula C5HONC13Na, molecular weight 220.5, sterling is white solid, is to close
Become insecticide chlorpyrifos, chlorpyrifos-methyl and the important intermediate of herbicide Triclopyr.Conjunction to trichloro pyridyl sodium alcoholate both at home and abroad
Becoming technique to carry out substantial amounts of research, the initiation material according to being used divides, and mainly has pyridine method and cyclization method two main road
Line.
Pyridine method is divided into again pyridine derivate method and pyridine chlorination method.Pyridine derivate method is i.e. that first synthesis is containing multiple
The pyridine derivate of substituent group, then remove unnecessary substituent group by the method such as reduction, or substituent group is converted into Cl or-
OH, thus obtain phenolate trichloropyridine.Pyridine chlorination method be pyridine in the presence of a catalyst, through high temperature gas phase chlorination generate pentachloro-pyrrole
Pyridine, then be 4 chloro pyridine through selective reduction, i.e. obtain phenolate trichloropyridine or its sodium salt after being acidified or hydrolyzing.
Cyclization method is broadly divided into trichloro-acetic chloride method, trichloroacetic acid phenyl ester method and acryloyl chloride method.Trichloroacetic acid phenyl ester method
Be trichloroacetic acid phenyl ester in the presence of the catalyst such as Cu-lyt., with dry sulpholane as solvent, obtain 2 in acrylonitrile addition,
2,4-tri-chloro-4-cyano butyric acid phenyl esters, then cyclization and aromatisation generate pyridol in the presence of dry hydrogen chloride.Acryloyl chloride
Method is acrylic acid and Phosphorous chloride. reaction prepares acryloyl chloride, then adds with Tritox and become 2,2,4-tri-chloro-4-cyano group butyryl
Chlorine, then cyclization becomes 3 in the presence of a catalyst, 5,5,6-tetra-chloro-dihydropyridine-2-ketone, last aromatization chemical conversion pyridol.
Trichloro-acetic chloride method can be divided into again " one kettle way " and the method for fractional steps.Patent CN 104177291 A with trichloro-acetic chloride and
Acrylonitrile is raw material, and Cu-lyt. tetrabutylammonium chloride is catalyst, is subsequently adding promoter, by addition, cyclization and virtue
Structure reaction profile prepares 3,5,6-trichloropyridine-2-sodium alkoxide, although the method reaches higher yield 80%, but technical process
Long, reactions steps is loaded down with trivial details, and wastewater flow rate is big, does not meets the requirement of low cost and environmental protection.Patent CN 105348178 A is with three
Chloracetyl chloride and acrylonitrile are raw material, under the effect of specific solvent and special catalyst, obtain through addition cyclization one-step method
3,3,5,6-tetra-chloro-4,4-dihydropyridine-2-ketone, then obtain 3 by precipitation, crystallization, alkali analysis, 5,6-trichloropyridine-2-sodium alkoxide,
The method addition time-consuming 24-38h of cyclization process, the response time is long, and selectivity and yield do not reach reported theoretical value.
Summary of the invention
It is an object of the invention to provide one and prepare 3, the method for 5,6-trichloropyridine-2-sodium alkoxide, to solve the above-mentioned back of the body
The problem proposed in scape technology.
For achieving the above object, the present invention provides following technical scheme:
Route of the present invention is that " one kettle way " synthesizes 3,5,6-trichloropyridine-2-sodium alkoxide, with trichloro-acetic chloride and
Acrylonitrile is raw material, and under the effect of specific solvent and special catalyst, reaction is carried out in a reactor, and a step obtains 3,
3,5,6-4 chloro pyridine-4,4-dihydropyridine-2-ketone, then obtain 3 through alkali analysis, 5,6-trichloropyridine-2-sodium alkoxide.
One prepares 3, the method for 5,6-trichloropyridine-2-sodium alkoxide, specifically comprises the following steps that
(1) trichloro-acetic chloride and acrylonitrile are put in mixed solvent, at CuCl2In the presence of catalyst A, it is warming up to
110～130 DEG C carry out back flow reaction 10～14h；
(2), after backflow terminates, in reactor, add the liquid caustic soda that mass fraction is 28～32%, regulate pH=9～12,
Carry out aromatization 3～5h at 30～55 DEG C, fully after reaction, be filtrated to get trichloro pyridyl sodium alcoholate crude product；
(3) the trichloro pyridyl sodium alcoholate crude product of gained is put into equipped with water, catalyst B, alkali reactor in, temperature rising reflux
1.8～2.2h, then sucking filtration, be dried, obtain high-purity trichloro pyridyl sodium alcoholate finished product.
As the further scheme of the present invention: in described step (1), trichloro-acetic chloride with the molar ratio of acrylonitrile is
1:1.1～1.5.
As the further scheme of the present invention: in described step (1), mixed solvent used is Benzene Chloride, o-dichlorohenzene, second
In acid butyl ester, toluene, o-Dimethylbenzene, xylol, Nitrobenzol, sulfolane 2 kinds.
As the further scheme of the present invention: in described step (1), trichloro-acetic chloride is 1 with the mass ratio of mixed solvent:
1.8～2.0.
As the further scheme of the present invention: in described step (1), catalyst A is tetramethyl ammonium chloride, tetrabutyl chlorination
Ammonium, tetraethylammonium bromide, triphenylmethylphosphonium bromide phosphorus, benzyltrimethylammonium chloride, tetraphenylphosphonibromide bromide, benzyl triphenyl phosphonium chloride
In phosphine, tetrabutyl ammonium bromide, eight alkyl trimethyl amine bromides, tetramethyl ammonium hydrogen sulfate 2 kinds.
As the further scheme of the present invention: in described step (1), CuCl2With the mass ratio of catalyst A be 1:0.8～
1.4。
As the further scheme of the present invention: in described step (1), the quality of catalyst A is trichloro-acetic chloride
0.25%～0.5%.
As the present invention further scheme: in described step (3), catalyst B is benzyltrimethylammonium chloride, 4-first
Amido pyridine, N, N-lutidines, methyl-2-pyridine, benzyltriethylammoinium chloride, PEG-4000, tetrabutyl phosphonium bromide
The mixture of one or more in ammonium.
Compared with prior art, the invention has the beneficial effects as follows:
1, whole reaction is carried out in a reactor, without desolvation in subsequent handling, greatly reduces technique former
The cost of material and energy consumption, beneficially large-scale production；
2, additive reaction and ring-closure reaction occur simultaneously, it is to avoid be passed through HCl in the method for fractional steps to the corrosion of equipment and human body
Injury, reduces equipment cost；
3, under identical catalytic condition, catalyst A price is less than other phase transfer catalysts, through adjusting, at least saves
Production cost 30%；
4, subtractive process uses catalyst B and the cooperation of alkali, be greatly improved product purity to about 88%, and product face
Color is off-white color.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, all
Belong to the scope of protection of the invention.
Embodiment 1
Trichloro pyridyl sodium alcoholate building-up process is as follows:
(1) in the four-hole boiling flask of 2000mL, 655.2g mixed solvent (o-dichlorohenzene 327g, xylol are added
328.2g), 364g trichloro-acetic chloride, 116.6g acrylonitrile, 112.5gCuCl are added2With 90g catalyst A (tetraethyl bromination
Ammonium 20g and tetraphenylphosphonibromide bromide 70g), it is heated to 110 DEG C, back flow reaction 10h；
(2) after back flow reaction terminates, to be cooled, the liquid caustic soda adding 29% in reactor carries out aromatization, controls
Reaction temperature, at 30～40 DEG C, maintains pH to about 10, after fully reaction 4h, is filtrated to get sodium alkoxide crude product；
(3) above-mentioned trichloro pyridyl sodium alcoholate crude product is put into equipped with 1000g water, 0.5g PEG-4000,100g30% liquid
In the reactor of alkali, temperature rising reflux 2h, then sucking filtration, be dried, obtain off-white color trichloro pyridyl sodium alcoholate finished product 368.0g, yield reaches
83.1%.
Through the detection of HPLC, 3,5,6-trichloropyridine-2-sodium alkoxide purity are 88.5%.
Embodiment 2
Trichloro pyridyl sodium alcoholate building-up process is as follows:
(1) in the four-hole boiling flask of 2000mL, 680.7g mixed solvent (butyl acetate 273.6g, Nitrobenzol are added
407.1g), 364.6g trichloro-acetic chloride, 135.7g acrylonitrile, 120gCuCl are added2With 120g catalyst A (tetrabutyl chlorination
Ammonium 50g and tetraphenylphosphonibromide bromide 70g), it is heated to 110 DEG C, back flow reaction 14h；
(2) after back flow reaction terminates, to be cooled, the liquid caustic soda adding 30% in reactor carries out aromatization, controls
Reaction temperature, at 35～45 DEG C, maintains pH to about 11, after fully reaction 3h, is filtrated to get sodium alkoxide crude product；
(3) above-mentioned trichloro pyridyl sodium alcoholate crude product is put into equipped with 1000g water, 0.5g methyl-2-pyridine, 100g30% liquid caustic soda
Reactor in, temperature rising reflux 2h, then sucking filtration, be dried, obtain off-white color trichloro pyridyl sodium alcoholate finished product 365.8g, yield reaches
82.6%.
Through the detection of HPLC, 3,5,6-trichloropyridine-2-sodium alkoxide purity are 88.4%.
Embodiment 3
Trichloro pyridyl sodium alcoholate building-up process is as follows:
(1) in the four-hole boiling flask of 2000mL, 700g mixed solvent (butyl acetate 285.4g, Nitrobenzol 414.6g) is added,
Add 364.6g trichloro-acetic chloride, 138.3g acrylonitrile, 210gCuCl2With 150g catalyst A (tetrabutyl ammonium bromide 50g and
Eight alkyl trimethyl amine bromide 100g), it is heated to 130 DEG C, back flow reaction 12h；
(2) after back flow reaction terminates, to be cooled, the liquid caustic soda adding 31% in reactor carries out aromatization, controls
Reaction temperature, at 40～50 DEG C, maintains pH to about 12, after fully reaction 5h, is filtrated to get sodium alkoxide crude product；
(3) by above-mentioned trichloro pyridyl sodium alcoholate crude product put into equipped with 1000g water, 0.5g benzyltrimethylammonium chloride,
In the reactor of 100g30% liquid caustic soda, temperature rising reflux 2h, then sucking filtration, be dried, obtain off-white color trichloro pyridyl sodium alcoholate finished product
374.6g, yield 84.6%.
Through the detection of HPLC, 3,5,6-trichloropyridine-2-sodium alkoxide purity are 88.7%.
Embodiment 4
Trichloro pyridyl sodium alcoholate building-up process is as follows:
(1) to warding off of 2000mL, four-hole boiling flask adds 720g mixed solvent (Benzene Chloride 400g, sulfolane 320g), then add
Enter 364.4g trichloro-acetic chloride, 158.4g acrylonitrile, 212.8gCuCl2With 177.3g catalyst A (benzyltrimethylammonium chloride
114.1g and tetramethyl ammonium hydrogen sulfate 63.2g), it is heated to 125 DEG C, back flow reaction 13h；
(2) after back flow reaction terminates, to be cooled, the liquid caustic soda adding 30% in reactor carries out aromatization, controls
Reaction temperature, at 45～55 DEG C, maintains pH to 11～12, after fully reaction 3.5h, is filtrated to get sodium alkoxide crude product；
(3) by above-mentioned trichloro pyridyl sodium alcoholate crude product put into equipped with 1000g water, 0.5g benzyltriethylammoinium chloride,
In the reactor of 100g30% liquid caustic soda, temperature rising reflux 2h, then sucking filtration, be dried, obtain off-white color trichloro pyridyl sodium alcoholate finished product
364.9g, yield reaches 82.4%.
Through the detection of HPLC, 3,5,6-trichloropyridine-2-sodium alkoxide purity are 88.9%.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, it is possible to realize the present invention in other specific forms.Therefore, no matter
From the point of view of which point, all should regard embodiment as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all by fall in the implication of equivalency and scope of claim
Change is included in the present invention.
Claims (8)
1. prepare 3 for one kind, the method for 5,6-trichloropyridine-2-sodium alkoxide, it is characterised in that specifically comprise the following steps that
(1) trichloro-acetic chloride and acrylonitrile are put in mixed solvent, at CuCl2In the presence of catalyst A, be warming up to 110～
130 DEG C carry out back flow reaction 10～14h；
(2), after backflow terminates, adding mass fraction in reactor is the liquid caustic soda of 28～32%, regulates pH=9～12,30～
Carry out aromatization 3～5h at 55 DEG C, fully after reaction, be filtrated to get trichloro pyridyl sodium alcoholate crude product；
(3) the trichloro pyridyl sodium alcoholate crude product of gained is put into equipped with water, catalyst B, alkali reactor in, temperature rising reflux 1.8～
2.2h, then sucking filtration, be dried, obtain high-purity trichloro pyridyl sodium alcoholate finished product.
The method of preparation 3,5,6-trichloropyridine-2-sodium alkoxide the most according to claim 1, it is characterised in that described step
(1), in, trichloro-acetic chloride is 1:1.1～1.5 with the molar ratio of acrylonitrile.
The method of preparation 3,5,6-trichloropyridine-2-sodium alkoxide the most according to claim 1, it is characterised in that described step
(1), in, mixed solvent used is Benzene Chloride, o-dichlorohenzene, butyl acetate, toluene, o-Dimethylbenzene, xylol, Nitrobenzol, ring
In fourth sulfone 2 kinds.
The method of preparation 3,5,6-trichloropyridine-2-sodium alkoxide the most according to claim 1, it is characterised in that described step
(1), in, trichloro-acetic chloride is 1:1.8～2.0 with the mass ratio of mixed solvent.
The method of preparation 3,5,6-trichloropyridine-2-sodium alkoxide the most according to claim 1, it is characterised in that described step
(1) in, catalyst A is tetramethyl ammonium chloride, tetrabutylammonium chloride, tetraethylammonium bromide, triphenylmethylphosphonium bromide phosphorus, benzyl three
Ammonio methacrylate, tetraphenylphosphonibromide bromide, benzyl triphenyl phosphonium chloride phosphine, tetrabutyl ammonium bromide, eight alkyl trimethyl amine bromides, tetramethyl
In base ammonium hydrogen sulfate 2 kinds.
The method of preparation 3,5,6-trichloropyridine-2-sodium alkoxide the most according to claim 1, it is characterised in that described step
(1) in, CuCl2It is 1:0.8～1.4 with the mass ratio of catalyst A.
The method of preparation 3,5,6-trichloropyridine-2-sodium alkoxide the most according to claim 1, it is characterised in that described step
(1), in, the quality of catalyst A is the 0.25%～0.5% of trichloro-acetic chloride.
The method of preparation 3,5,6-trichloropyridine-2-sodium alkoxide the most according to claim 1, it is characterised in that described step
(3), in, catalyst B is benzyltrimethylammonium chloride, 4-picolilamine, N, N-lutidines, methyl-2-pyridine, benzyl
The mixture of one or more in triethyl ammonium chloride, PEG-4000, tetrabutyl ammonium bromide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216351A (en) * | 2017-08-09 | 2017-09-29 | 重庆华歌生物化学有限公司 | Chlopyrifos and preparation method thereof |
| CN109503470A (en) * | 2019-01-07 | 2019-03-22 | 江苏琦衡农化科技有限公司 | A kind of production technology of 3,5,6- trichloropyridine -2- sodium alkoxide of high-purity |
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| CN1970541A (en) * | 2005-11-22 | 2007-05-30 | 华东理工大学 | Method for preparing 3,5,6-trichloro pyridine-2-sodium alcoholate without solvent |
| CN102993237A (en) * | 2012-12-12 | 2013-03-27 | 江苏琦衡农化科技有限公司 | Aqueous-phase synthesis method of chlorpyrifos by using trichloro-acetic chloride as initial material |
| CN104177291A (en) * | 2014-07-23 | 2014-12-03 | 安徽国星生物化学有限公司 | Synthesis method of 3,5,6-trichloropyridyl-2-sodium alkoxide |
| CN104876858A (en) * | 2015-05-13 | 2015-09-02 | 安徽国星生物化学有限公司 | One-pot method for synthesizing sodium 3,5,6-trichloropyridin-2-olate |
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2016
- 2016-07-05 CN CN201610524597.9A patent/CN106187871A/en active Pending
Patent Citations (4)
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|---|---|---|---|---|
| CN1970541A (en) * | 2005-11-22 | 2007-05-30 | 华东理工大学 | Method for preparing 3,5,6-trichloro pyridine-2-sodium alcoholate without solvent |
| CN102993237A (en) * | 2012-12-12 | 2013-03-27 | 江苏琦衡农化科技有限公司 | Aqueous-phase synthesis method of chlorpyrifos by using trichloro-acetic chloride as initial material |
| CN104177291A (en) * | 2014-07-23 | 2014-12-03 | 安徽国星生物化学有限公司 | Synthesis method of 3,5,6-trichloropyridyl-2-sodium alkoxide |
| CN104876858A (en) * | 2015-05-13 | 2015-09-02 | 安徽国星生物化学有限公司 | One-pot method for synthesizing sodium 3,5,6-trichloropyridin-2-olate |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107216351A (en) * | 2017-08-09 | 2017-09-29 | 重庆华歌生物化学有限公司 | Chlopyrifos and preparation method thereof |
| CN109503470A (en) * | 2019-01-07 | 2019-03-22 | 江苏琦衡农化科技有限公司 | A kind of production technology of 3,5,6- trichloropyridine -2- sodium alkoxide of high-purity |
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