CN110172710A - A kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters - Google Patents
A kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters Download PDFInfo
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- CN110172710A CN110172710A CN201910299357.7A CN201910299357A CN110172710A CN 110172710 A CN110172710 A CN 110172710A CN 201910299357 A CN201910299357 A CN 201910299357A CN 110172710 A CN110172710 A CN 110172710A
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Abstract
A kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters disclosed by the invention, which is characterized in that the described method comprises the following steps: (1) more chloro-pyridine derivatives are dissolved in the alcohol or phenol solution containing electrolyte, obtain cell reaction liquid；(2) using the cell reaction liquid as catholyte, electroreduction dechlorination alcoholysis reaction is carried out in cathode, more chloro-pyridine carboxylic esters derivatives are obtained, more chloromethyl pyridine derivatives are as shown in the formula (I), and the more chloro-pyridine carboxylic esters derivatives of product are as shown in the formula (II):In formula (I), m 0,1,2,3 or 4；M and same formula (I), R C in formula (II)1—C8Alkyl, phenyl or the phenyl containing functional group, the beneficial effects are mainly reflected as follows: reaction a step can be completed at normal temperatures and pressures；Reaction process does not use the concentrated sulfuric acid, so as to avoid a large amount of intractable high COD acid waste liquids；Without using the thionyl chloride being more toxic and avoid generating sulfur dioxide gas.
Description
Technical field
The present invention relates to a kind of more chloromethyl pyridine derivative electrochemical fields, and in particular to a kind of trichloromethyl pyridine spreads out
The method that bioelectrochemistry dechlorination prepares carboxylic esters.
Background technique
Picolinic acid rouge is the important molecule segment of various new pesticide (such as fluorine chloropyridine ester and chlorine fluorine pyridine ester), because
This, the green of this substance, high efficiency preparation method are constantly subjected to the concern of enterpriser.
In the prior art, Chinese patent (201710993290.8) is disclosed with the fluoro- 6- trifluoromethyl-acidum nicotinicum of 4-
For raw material, acylation reaction first is carried out with chlorination reagent, the method for corresponding picolinic acid rouge is then prepared with alcohol esterification reaction.Zheng Hui
The hydrolysis that sulfuric acid is catalyst is first passed through using pyridine first cyanogen as raw material etc. reporting, and then carries out acyl chlorides with thionyl chloride
Change reaction, the method for finally preparing picolinic acid rouge with alcohol esterification reaction；BASF European Co., Ltd obtains the Chinese patent of authorization
(200680041607.8) it discloses using trichloromethyl pyridine derivative as raw material, first in 110-160 DEG C of concentrated sulfuric acid solution
Acid chloride intermediate is prepared in middle progress acylation reaction, then obtains the side of corresponding picolinic acid rouge in alcoholic solution alcoholysis
Method.
However, above-mentioned reaction exists using the thionyl chloride toxicant being more toxic, and it is also easy to produce a large amount of acid waste liquid,
Preparation condition is dangerous.
Summary of the invention
To solve the above problems, the present invention, which provides a kind of trichloromethyl pyridine derivative electrochemistry dechlorination, prepares carboxylic esters
Method.The advantages that this method reaction condition and process are simple, pollution is small.
The technical solution that the present invention solves is to provide a kind of trichloromethyl pyridine derivative electrochemistry dechlorination and prepares carboxylate
Method, which is characterized in that the described method comprises the following steps:
(1) more chloro-pyridine derivatives are dissolved in the alcohol or phenol solution containing electrolyte, obtain cell reaction liquid；
(2) using the cell reaction liquid as catholyte, electroreduction dechlorination alcoholysis reaction is carried out in cathode, obtains more chloro-pyridines
Carboxylic esters derivative.
More chloromethyl pyridine derivatives are as shown in the formula (I), the more chloro-pyridine carboxylic esters derivative such as formula (II)s of product
It is shown:
In formula (I), m 0,1,2,3 or 4；M and same formula (I), R C in formula (II)1—C8Alkyl, phenyl or containing functional group
Phenyl.
Preferably, the cation of electrolyte is lithium ion, ammonium ion, tetramethyl ammonium root, tetraethyl ammonium root, tetrapropyl ammonium
One of root, tetrabutyl ammonium root are several；Anion is acetate, perchlorate, tetrafluoroborate one or several kinds.
Preferably, the pure and mild phenol is respectively C1—C8Alkylol and phenol and phenol containing functional group.
Preferably, the cathode is porous silver electrode or copper electrode, and the anode is zinc electrode, magnesium electrode or aluminium electrode
One of.
Preferably, the current density in the step (2) is 1-15 A/m2。
Preferably, cell reaction temperature is 25-70 DEG C in the step (2).
Preferably, the cell reaction liquid includes dissolved oxygen.
Preferably, the electrolyte includes the trichloromethyl pyridine derivative of 0.1-2 mol/L, 0.001-2 mol/L's
Electrolyte, the oxygen of 20-100 wt% dissolution saturation, 0.2-3 mol/L alcohol or phenol.
In the present solution, the cation of the electrolyte is lithium ion, ammonium ion, tetramethyl ammonium root, tetraethyl ammonium root, four
Propyl ammonium root, tetrabutyl ammonium root；Anion is acetate, perchlorate, tetrafluoroborate.Specifically, electrolyte can be
Lithium acetate, ammonium acetate, tetramethyl ammonium perchlorate (TMAP), tetraethyl ammonium perchlorate (TEAP), tetrapropyl ammonium perchlorate (TBAP),
Tetrabutylammonium perchlorate (TBAP), tetramethyl ammonium tetrafluoroborate (TMAT), tetraethyl ammonium tetrafluoroborate (TEAT), tetrapropyl tetrafluoro
Ammonium borate (TPAT), tetrabutyl ammonium tetrafluoroborate (TBAT) and their mixture.The alcohol or phenol are as follows: methanol, ethyl alcohol, just
Propyl alcohol, isopropanol, cyclohexanol, adamantanol, phenol, fluorophenol；The electrochemistry preparation reaction temperature is 25-70 DEG C.It is excellent
The temperature of choosing depends on solvent, for example methanol is solvent, and preferred temperature is 25-30 DEG C；Acetonitrile is solvent, and preferred temperature is
65-70 ℃。
Trichloromethyl pyridine derivative shown in formula (I) of the present invention includes: 2- chloro-5-trichloromethylpyridine, the chloro- 3- of 2-
Trichloromethyl pyridine, N-serve, 2,3- tri- chloro-5-trichloromethylpyridines, 2,3,4,5- chloro- tri- chloromethanes of 6-
Yl pyridines, the chloro- 4- trichloromethyl pyridine of 2-.
Cell reaction of the present invention can be carried out intermittently or be carried out in a continuous or semi-continuous manner.Electrolytic cell, which can be, to be contained
There are the stirred tank of electrode or the flow cell channel of any traditional design.Electrolytic cell can be single chamber slot can also with diaphragm cell,
It is preferred that single chamber slot.
The present invention carries out required electroreduction alcoholysis by one conventionally known in the art.Its mechanism is as follows:
Anode:
Cathode:
The carbonyl carbon of acyl chlorides is electron deficient carbon, it is easy to generate acyl compounds with the nucleopilic reagent in solvent, reaction process is first
It is that nucleophilic group adds in carbonyl carbon, negative group of then leaving away again.Contain alcohol or phenol, methoxyl group, ethyoxyl in electrolyte
Or hydroxyl adds to the carbonyl carbon of acyl chlorides, obtains carboxylate.
Generally, raw material trichloromethyl pyridine derivative is dissolved or is partially dissolved in solvent, be added a certain amount of
Supporting electrolyte and alcohol or phenol, enough electric currents are then passed through in electrolytic cell (can be with constant current either electric current stage by stage
The constant current of reduction, can also be with constant potential), until obtaining the reduction of required degree.Air is passed through in electrolytic process in electrolyte
Or oxygen, after cell reaction, product is recycled using traditional technology.It is easily waved for example, being steamed first with the method for distillation
Then the organic solvent (such as methanol) of hair is extracted to extraction raffinate is steamed with toluene, is finally obtained with the method for rectifying or recrystallization
To required product.
Compared with prior art, the beneficial effects are mainly reflected as follows: (1) reaction can at normal temperatures and pressures a step it is complete
At；(2) reaction process does not use the concentrated sulfuric acid, so as to avoid a large amount of intractable high COD acid waste liquids；(3) toxicity is not used
Biggish thionyl chloride and avoid generate sulfur dioxide gas.
Specific embodiment
The following is specific embodiments of the present invention, and technical scheme of the present invention will be further described, but the present invention is simultaneously
It is not limited to these embodiments.
All embodiments and the efficient liquid phase chromatographic analysis condition of comparative example are all are as follows:: C18 symmetrical posts (250 mm length
_ 4.6 mm i.d., 5 mm particle size) it is splitter；Acetonitrile/methanol/water (volume ratio 1:3:6) mixed solution
For mobile phase；Flow velocity are as follows: 1 mL/Min；Detection wavelength is 230 nm；2996 PDA of Waters is detector.
Embodiment 1
It is electrolysed 2- chloro-5-trichloromethylpyridine (TCP) and prepares 6- chlorine apellagrin methyl esters
Beaker is reactor, and silver-colored net is cathode, and zinc metal sheet is anode.+ 1.0 mol/L acetic acid of 200 mL, 0.5 mol/L TCP
The methanol solution of lithium is electrolyte.Oxygen is passed through in electrolytic process in electrolyte, temperature control is 20-25 DEG C, current density control
It is made as 1A/dm2.Stop electrolysis after being passed through 6 F/mol TCP electricity.It is obtained to after catholyte dilution with high-efficient liquid phase analysis with methanol
Arrive: TCP conversion ratio is 98 %, and the yield of 6- chlorine apellagrin methyl esters is 92%.
Embodiment 2
It is electrolysed 2- chloro-5-trichloromethylpyridine (TCP) and prepares 6- chlorine apellagrin methyl esters
Beaker is reactor, and silver-colored net is cathode, and zinc metal sheet is anode.+ 1.0 mol/L acetic acid of 200 mL, 0.5 mol/L TCP
The methanol solution of lithium is electrolyte.Oxygen is passed through in electrolytic process in electrolyte, temperature control is 60-70 DEG C, current density control
It is made as 15 A/dm2.Stop electrolysis after being passed through 6 F/mol TCP electricity.High-efficient liquid phase analysis is used after being diluted with methanol to catholyte
Obtain: TCP conversion ratio is 96 %, and the yield of 6- chlorine apellagrin methyl esters is 94%.
Embodiment 3
It is electrolysed 2- chloro-5-trichloromethylpyridine (TCP) and prepares 6- chlorine apellagrin methyl esters
Beaker is reactor, and silver-colored net is cathode, and zinc metal sheet is anode.+ 1.0 mol/L acetic acid of 200 mL, 0.5 mol/L TCP
The methanol solution of lithium is electrolyte.Oxygen is passed through in electrolytic process in electrolyte, temperature control is 60-70 DEG C, current density control
It is made as 10 A/dm2.Stop electrolysis after being passed through 6 F/mol TCP electricity.High-efficient liquid phase analysis is used after being diluted with methanol to catholyte
Obtain: TCP conversion ratio is 95 %, and the yield of 6- chlorine apellagrin methyl esters is 98%.
Comparative example 1
It is electrolysed 2- chloro-5-trichloromethylpyridine (TCP) and prepares 6- chlorine apellagrin
Beaker is reactor, and silver-colored net is cathode, and zinc metal sheet is anode.+ 1.0 mol/L acetic acid of 200 mL, 0.5 mol/L TCP
The methanol solution of lithium is electrolyte.Nitrogen is passed through in electrolytic process in electrolyte, temperature control is 20-25 DEG C, current density control
It is made as 5 A/dm2.Stop electrolysis after being passed through 6 F/mol TCP electricity.High-efficient liquid phase analysis is used after being diluted with methanol to catholyte
Obtain: TCP conversion ratio is 25 %, and the yield of 6- chlorine apellagrin methyl esters is 2%.
Comparative example 2
It is electrolysed 2- chloro-5-trichloromethylpyridine (TCP) and prepares 6- chlorine apellagrin methyl esters
Beaker is reactor, and silver-colored net is cathode, and zinc metal sheet is anode.+ 1.0 mol/L acetic acid of 200 mL, 0.5 mol/L TCP
The methanol solution of lithium is electrolyte.Oxygen is not passed through in electrolytic process in electrolyte, temperature control is 60-70 DEG C, current density
Control is 0 A/dm2.Same time stops reaction.Obtained to after catholyte dilution with high-efficient liquid phase analysis with methanol: TCP turns
Rate is 1 %, and the yield of 6- chlorine apellagrin methyl esters is 0 %.
Embodiment 2- embodiment 14
Embodiment 2- embodiment 14 is carried out according to the experiment parameter of table 1, remaining operation is the same as embodiment 1.
1 1000mL scale of table electrolysis 2- chloro-5-trichloromethylpyridine (TCP) prepare the experiment condition of 6- chlorine apellagrin rouge with
As a result
Embodiment 18- embodiment 22
Embodiment 18- embodiment 22 is carried out according to the experiment parameter of table 2, remaining operation is the same as embodiment 1.
2 200 mL scale of table is electrolysed experiment condition and result that various trichloromethyl pyridine derivatives prepare corresponding rouge
It is not directed to place above, is suitable for the prior art.
Specific embodiment described herein is only an example for the spirit of the invention.The neck of technology belonging to the present invention
The technical staff in domain can make various modifications or additions to the described embodiments or replace by a similar method
In generation, however, it does not deviate from the spirit of the invention or beyond the scope of the appended claims.
Claims (8)
1. a kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters, which is characterized in that the method packet
Include following steps:
More chloro-pyridine derivatives are dissolved in the alcohol or phenol solution containing electrolyte, obtain cell reaction liquid；
Using the cell reaction liquid as catholyte, electroreduction dechlorination alcoholysis reaction is carried out in cathode, obtains more chloro-pyridine carboxylics
Sour rouge derivative；
More chloromethyl pyridine derivatives are as shown in the formula (I), and the more chloro-pyridine carboxylic esters derivatives of product are as shown in the formula (II):
In formula (I), m 0,1,2,3 or 4；M and same formula (I), R C in formula (II)1—C8Alkyl, phenyl or containing functional group
Phenyl.
2. a kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters according to claim 1,
It is characterized in that, the cation of electrolyte is lithium ion, ammonium ion, tetramethyl ammonium root, tetraethyl ammonium root, tetrapropyl ammonium root, four
One of butyl ammonium root is several；Anion is acetate, perchlorate, tetrafluoroborate one or several kinds.
3. a kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters according to claim 1,
It is characterized in that, the pure and mild phenol is respectively C1—C8Alkylol and phenol and phenol containing functional group.
4. a kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters according to claim 1,
It is characterized in that, the cathode is porous silver electrode or copper electrode, and the anode is one in zinc electrode, magnesium electrode or aluminium electrode
Kind.
5. a kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters according to claim 1,
It is characterized in that, the current density in the step (2) is 1-15 A/m2。
6. a kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters according to claim 1,
It is characterized in that, cell reaction temperature is 25-70 DEG C in the step (2).
7. a kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters according to claim 1,
It is characterized in that, the cell reaction liquid includes dissolved oxygen.
8. a kind of method that the electrochemistry dechlorination of trichloromethyl pyridine derivative prepares carboxylic esters according to claim 1,
It is characterized in that, trichloromethyl pyridine derivative of the electrolyte comprising 0.1-2 mol/L, the electrolyte of 0.001-2 mol/L,
The oxygen of 20-100 wt% dissolution saturation, 0.2-3 mol/L alcohol or phenol.
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| CN201910299357.7A CN110172710B (en) | 2019-04-15 | 2019-04-15 | Method for preparing carboxylic ester by electrochemical dechlorination of trichloromethylpyridine derivative |
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| CN201910299357.7A CN110172710B (en) | 2019-04-15 | 2019-04-15 | Method for preparing carboxylic ester by electrochemical dechlorination of trichloromethylpyridine derivative |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114204106A (en) * | 2021-03-31 | 2022-03-18 | 松山湖材料实验室 | Lithium ion battery electrolyte additive, electrolyte and lithium ion battery |
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|---|---|---|---|---|
| CN105887128A (en) * | 2016-05-16 | 2016-08-24 | 浙江工业大学 | Method for electrical-catalytic and selective hydrogenating and dechlorinating of pentachloropyridine |
| CN105887127A (en) * | 2016-05-16 | 2016-08-24 | 浙江工业大学 | Method for preparing chloromethyl pyridine derivative by electrochemical selective dechloridation |
| CN105887129A (en) * | 2016-05-16 | 2016-08-24 | 浙江工业大学 | Method for preparing picoline derivative through electrochemistrical selective dechlorination of trichloromethyl pyridine derivative |
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2019
- 2019-04-15 CN CN201910299357.7A patent/CN110172710B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105887128A (en) * | 2016-05-16 | 2016-08-24 | 浙江工业大学 | Method for electrical-catalytic and selective hydrogenating and dechlorinating of pentachloropyridine |
| CN105887127A (en) * | 2016-05-16 | 2016-08-24 | 浙江工业大学 | Method for preparing chloromethyl pyridine derivative by electrochemical selective dechloridation |
| CN105887129A (en) * | 2016-05-16 | 2016-08-24 | 浙江工业大学 | Method for preparing picoline derivative through electrochemistrical selective dechlorination of trichloromethyl pyridine derivative |
Non-Patent Citations (1)
| Title |
|---|
| HISASHI SHIMAKOSHI ET AL.: "Electrolysis of trichloromethylated organic compounds under aerobic conditions catalyzed by the B12 model complex for ester and amide formation", 《DALTON TRANSACTIONS》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114204106A (en) * | 2021-03-31 | 2022-03-18 | 松山湖材料实验室 | Lithium ion battery electrolyte additive, electrolyte and lithium ion battery |
| CN114204106B (en) * | 2021-03-31 | 2023-10-20 | 松山湖材料实验室 | Electrolyte additive for lithium ion battery, electrolyte and lithium ion battery |
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