CN105712879B - A kind of preparation method of the carboxylate containing trifluoromethyl - Google Patents
A kind of preparation method of the carboxylate containing trifluoromethyl Download PDFInfo
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- CN105712879B CN105712879B CN201410734762.4A CN201410734762A CN105712879B CN 105712879 B CN105712879 B CN 105712879B CN 201410734762 A CN201410734762 A CN 201410734762A CN 105712879 B CN105712879 B CN 105712879B
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Abstract
The invention discloses a kind of preparation methods of carboxylate containing trifluoromethyl, first make haloformate X3COOR2With alkenyl halide R1=CX1X2Reaction preparation X1X2X3CR1COOR2, preparation CF is further reacted with fluorination reagent3R1COOR2.Method provided by the invention has the advantages that low cost, high yield, the CF of preparation3R1COOR2Suitable for lithium-ion battery electrolytes.
Description
Technical field
The present invention relates to a kind of preparation methods of carboxylate, more particularly, to a kind of preparation side containing trifluoromethyl carboxylates
Method.
Background technique
Carboxylate containing trifluoromethyl as fluorine ester, both may be used as reaction dissolvent, synthesis medicine, pesticide or its
The intermediate of his high-performance fluorine-containing material, can also be used as electrolyte solvent or electrolysis additive is applied to lithium ion battery.
Carboxylate electrochemical stability containing trifluoromethyl is good, electrochemical window is up to 5V or more, and cost is reasonable, this makes
It can be used for lithium ion battery high-voltage electrolyte as electrolyte solvent.The carboxylate containing trifluoromethyl has viscosity simultaneously
Low feature can reduce the viscosity of electrolyte at low temperature when it is used as additive, improve lithium ion transport rate, from
And improve the cryogenic property of battery, therefore it can also be used for low temperature electrolytes for Li-ion batteries as electrolyte solvent.Furthermore contain
The carboxylate flash-point of trifluoromethyl is high, can also be used as flame-retardant additive applied to lithium ion battery.
In the prior art the preparation method to the carboxylate containing trifluoromethyl mainly include the following types:
Document Journal of Fluorine Chemistry 129 (2008): 35-39 use the carboxylic acid containing trifluoromethyl
The carboxylate containing trifluoromethyl is prepared by esterification with alcohol, but since the carboxylic acid containing trifluoromethyl is difficult to prepare, and price
It is higher, such as trifluoroacetic acid, need the trifluoro propene to be difficult to obtain to prepare as raw material by three-step reaction, this considerably increases contain
The preparation cost of the carboxylate of trifluoromethyl further hinders its application in high-voltage electrolyte, constrains high voltage
The further development of lithium ion battery.
Chinese patent CN 103145556A is also disclosed using the higher trifluoro propene of price as raw material, through two-step reaction
The method for preparing trifluoroacetic acid methyl esters.This method not only raw material trifluoro propene price and it is necessary to be urged using expensive palladium carbon
Agent is unfavorable for industrialized production.
United States Patent (USP) US 4582924 discloses a kind of method for preparing trifluoroacetic acid methyl esters as raw material using octafluoroisobutene,
Through two-step reaction, yield about 67%.More bronsted lowry acids and bases bronsted lowry is used in reaction, the three wastes of generation are more, and octafluoroisobutene
It is more toxic, is unfavorable for industrialized production.
Therefore, it is necessary to develop a kind of new preparation method containing trifluoromethyl carboxylates.
Summary of the invention
The purpose of the present invention is to provide a kind of methods prepared containing trifluoromethyl carboxylates, have low cost, high yield
The advantages of.
To reach goal of the invention the technical solution adopted by the present invention is that:
A kind of preparation method of the carboxylate containing trifluoromethyl, comprising the following steps:
(1) in the presence of an organic, haloformate X3COOR2With alkenyl halide R1=CX1X2It reacts and prepares for raw material
Intermediate product shown in structure formula (I) (I)
Wherein:
R1Selected from-CH2、-CHCH3、-CF2、-CHCF3Or-CHCH2CF3；
R2Selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH(CH3)CH3、-CH2CH(CH3)CH3、-CH
(CH3)CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3Or-CH2CH2(CH2CH3)CH2CH2CH2CH3；
X1、X2And X3Independently selected from F, Cl, Br, I；
(2) in the presence of an organic, under the action of catalyst, intermediate product (I) reacts preparation structure with fluorination reagent
Carboxylate containing trifluoromethyl shown in formula (II),
The fluorination reagent is in potassium fluoride, cesium fluoride, zinc fluoride, copper fluoride, lithium fluoride, sodium fluoride and hydrogen fluoride
A kind of, two or three of combination of the above；
The catalyst is selected from benzyltriethylammoinium chloride (TEBA), four (diethylin) ethylene (TDAE) and bis- (triphens
Base phosphine) close rhodium carbonyl chloride (RhCl (CO) (PPh3)2) one of, two or three.
As preferred mode, in above-mentioned intermediate product (I) and carboxylate containing trifluoromethyl, R1It preferably is selected from-CH2、-
CHCH3、-CF2Or-CHCF3, R2It preferably is selected from-CH3、-CH2CH3Or-CH2CH2CH3, X1、X2And X3Independently it preferably is selected from F or Cl.
As preferred mode, above-mentioned fluorination reagent preferably is selected from one in potassium fluoride, cesium fluoride, zinc fluoride and hydrogen fluoride
Kind, two or three of combination of the above；Above-mentioned organic solvent preferably is selected from methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, acetic acid
Propyl ester, butyl acetate, dimethyl carbonate, diethyl carbonate or with one of petroleum ether, two or three of combination of the above.
As preferred mode, above-mentioned haloformate X3COOR2With alkenyl halide R1=CX1X2Mol ratio be preferably
1:1~1:9, and further preferably 1:1~1:5；The mol ratio of above-mentioned intermediate product (I) and fluorination reagent is preferably 1:1
~1:9, and further preferably 1:1~1:5；The mol ratio of above-mentioned intermediate product (I) and catalyst be preferably 1:0.005~
1:0.05, and further preferably 1:0.005~1:0.01.
As preferred mode, the reaction temperature of above-mentioned steps (1) is -10 DEG C~70 DEG C, the reaction temperature of step (2)
It is -10 DEG C~100 DEG C.As further preferred mode, the reaction temperature of above-mentioned steps (I) is -10 DEG C~40 DEG C, step
(2) reaction temperature is 0 DEG C~60 DEG C.
Specific embodiment
The following examples are but not limit the invention to this for illustrating several specific embodiments of the invention
A little specific embodiments.One skilled in the art would recognize that present invention encompasses may wrap in Claims scope
All alternatives, improvement project and the equivalent scheme included.
Embodiment 1
141.8g (1.5mol) methylchloroformate and 200ml methylene chloride are added in 500ml there-necked flask, leads at 0 DEG C
Enter vinylidene, when vinylidene does not reabsorb, stops reaction, 10% hydrochloric acid is added, being extracted with dichloromethane therein has
Machine object, organic layer are washed with successively 10% hydrochloric acid, 10% aqueous sodium carbonate, saturated aqueous sodium chloride, dry with magnesium sulfate.
It boils off solvent and obtains product dichloro fluorine methyl propionate 197.4g, yield 83%.
Dichloro fluorine methyl propionate 158.6g (1.0mol), methylene chloride 200ml, potassium fluoride are added in 500ml there-necked flask
174.3g (3.0mol), TEBA 8.0g are stirred 12 hours under room temperature, are filtered, and evaporation of solvent obtains trifluoroacetic acid methyl esters
106.5g yield 75%.
Embodiment 2
10.9g (0.1mol) ethyl chloroformate and 50ml methylene chloride are added in 100ml there-necked flask, is added dropwise at 10 DEG C
10.2g (0.105mol) vinylidene chloride reacts 5 hours after being added dropwise.12% hydrochloric acid is added, is extracted with dichloromethane therein
Organic matter, organic layer are washed with successively 12% hydrochloric acid, 10% aqueous sodium carbonate, saturated aqueous sodium chloride, dry with magnesium sulfate
It is dry.It boils off solvent and obtains product chloropon ethyl ester 12.9g, yield 63%.
Chloropon ethyl ester 12.3g (0.06mol), methylene chloride 50ml, cesium fluoride are added in 100ml there-necked flask
45.6g (0.3mol), TEBA 1.2g are stirred 12 hours under room temperature, are filtered, and evaporation of solvent obtains trifluoroacetic acid ethyl ester
(Mw=156.1) 12.3g, yield 79%.
Embodiment 3
60.2g (0.4mol) amyl chlorocarbonate and 400ml methylene chloride are added in 1000ml there-necked flask, is dripped at 60 DEG C
Add 44.4g (0.4mol) dichloropropylene, is reacted 10 hours after being added dropwise.8% hydrochloric acid is added, is extracted with dichloromethane therein
Organic matter, organic layer are washed with successively 8% hydrochloric acid, 8% aqueous sodium carbonate, saturated aqueous sodium chloride, dry with magnesium sulfate.
It boils off solvent and obtains product trichlorobutyric acid pentyl ester (Mw=261.61) 73.3g, yield 70%.
Trichlorobutyric acid pentyl ester 76.3g (0.28mol), methylene chloride 500ml, zinc fluoride are added in 1000ml there-necked flask
43.4g (0.42mol), TDBA 7.5g are stirred 6 hours at 60 DEG C, are filtered, evaporation of solvent obtains trifluoroacetic acid pentyl ester
(Mw=212) 50.5g, yield 85%.
Embodiment 4
55.58g (0.4mol) bromine methyl formate and 450ml ethyl acetate are added in 1000ml there-necked flask, is dripped at 0 DEG C
Add 52.2g (0.4mol) trifluoro chloropropene, is reacted 3 hours after being added dropwise.10% hydrochloric acid is added, is extracted with dichloromethane wherein
Organic matter, organic layer washs with successively 10% hydrochloric acid, 5% aqueous sodium carbonate, saturated aqueous sodium chloride, dry with magnesium sulfate
It is dry.It boils off solvent and obtains the chloro- 3- of product 3- bromo- 4,4,4 ,-trifluoromethyl butyrate (Mw=269.45) 88.4g, yield 82%.
The chloro- 3- of 3- bromo- 4,4,4 ,-trifluoromethyl butyrate 88.4g (0.328mol), acetic acid are added in 1000ml there-necked flask
Ethyl ester 500ml, zinc fluoride 43.4g (0.42mol), TDBA 4.5g are stirred 6 hours at 60 DEG C, are filtered, evaporation of solvent obtains
To 3,3,4,4,4- five fluorine methyl butyrate (Mw=192.06) 56.7g, yield 90%.
Embodiment 5
16.7g (0.1mol) bromine propyl formate and 100ml chloroform are added in 250ml there-necked flask, is passed through difluoro at 0 DEG C
Dichloroethylene stops reaction when dichlorodifluoroethylene does not reabsorb.10% hydrochloric acid is added, is extracted with chloroform therein organic
Object, organic layer successively 15% hydrochloric acid, 15% sodium bicarbonate aqueous solution, chlorination saturation sodium water solution wash, dry with magnesium sulfate.
It boils off solvent and obtains product 2, bis- chloro- 3- bromo-propionic acid propyl ester (Mw=299.92) 25.5g of fluoro- 3,3- bis- of 2-, yield 85%.
The bis- chloro- 3- bromo-propionic acid propyl ester 25.5g (0.085mol) of fluoro- 3,3- bis- of 2,2-, chloroform are added in 250ml there-necked flask
500ml, sodium fluoride 12.8g (0.30mol), TDBA 4.5g are stirred 12 hours at 40 DEG C, are filtered, boil off solvent, obtain 2,2,
3,3,3- five fluorine propyl propionate (Mw=206.08) 16.1g, yield 92%.
Embodiment 6
13.66g (0.1mol) butyl chlorocarbonate and 40ml propyl acetate are added in 100ml there-necked flask, is dripped at 10 DEG C
Add 16.65g (0.15mol) dichloropropylene, is reacted 5 hours after being added dropwise.20% hydrochloric acid, organic layer successively 20% salt is added
Acid, the washing of 10% aqueous sodium carbonate, saturated aqueous sodium chloride, it is dry with magnesium sulfate.It boils off solvent and obtains product 2- methyl-
Chloro- 3- bromo-propionic acid butyl ester (Mw=247.58) 16.09g of 3-, yield 65%.
The chloro- 3- bromo-propionic acid butyl ester 16.09g (0.065mol) of 2- methyl -3-, propyl acetate are added in 100ml there-necked flask
40ml, copper fluoride 13.20g (0.13mol), TEBA 1.2g are stirred 10 hours at 40 DEG C, are filtered, boil off solvent, obtain 2- first
Base-trifluoroacetic acid butyl ester (Mw=198.1) 9.01g, yield 70%.
Embodiment 7
38.54g (0.2mol) chloro-carbonic acid -2- ethylhexyl and 250ml dimethyl carbonate are added in 500ml there-necked flask,
38.78g (0.4mol) vinylidene chloride is added dropwise at 0 DEG C, is reacted 5 hours after being added dropwise.10% hydrochloric acid is added, uses dichloromethane
Alkane extracts organic matter therein, and organic layer is washed with successively 10% hydrochloric acid, 15% aqueous sodium carbonate, saturated aqueous sodium chloride
It washs, it is dry with magnesium sulfate.It boils off solvent and obtains product chloropon -2- ethylhexyl (Mw=289.62) 44.02g, yield
76%.
Chloropon -2- ethylhexyl 43.44g (0.15mol), dimethyl carbonate are added in 500ml there-necked flask
200ml, cesium fluoride 91.14g (0.60mol), TDBA 2.5g, 70 DEG C are stirred 5 hours, and filtering boils off solvent, obtains trifluoropropyl
Acid -2- ethylhexyl (Mw=240.27) 29.19g, yield 81%.
Embodiment 8
13.66g (0.1mol) isobutyl chlorocarbonate and 40ml petroleum ether are added in 100ml there-necked flask, is passed through at 0 DEG C
Vinylidene fluoride stops reaction when vinylidene fluoride does not reabsorb.It is added 10% hydrochloric acid, organic layer successively 6% hydrochloric acid,
5% aqueous sodium carbonate, saturated aqueous sodium chloride washing, it is dry with magnesium sulfate.It boils off solvent and obtains product 3,3,3- difluoro
One chloropropionic acid isobutyl ester (Mw=200.63) 12.04g, yield 60%.
One chloropropionic acid butyl ester 12.04g (0.06mol) of 3,3,3- difluoro, propyl acetate are added in 100ml there-necked flask
40ml, potassium fluoride 6.97g (0.12mol), TEBA 1.0g are stirred 5 hours at 50 DEG C, are filtered, boil off solvent, obtain trifluoropropyl
Sour isobutyl ester (Mw=184.18) 9.72g, yield 88%.
Embodiment 9
138.1g (1.5 mol) methylfluoracetate and 200ml methylene chloride are added in 500ml there-necked flask, leads at 0 DEG C
Enter vinylidene, when vinylidene does not reabsorb, stops reaction, 10% hydrochloric acid is added, being extracted with dichloromethane therein has
Machine object, organic layer are washed with successively 10% hydrochloric acid, 10% aqueous sodium carbonate, saturated aqueous sodium chloride, dry with magnesium sulfate.
It boils off solvent and obtains product trifluoromethyl butyrate 187.2g, yield 80%.
Claims (10)
1. a kind of preparation method of the carboxylate containing trifluoromethyl, it is characterised in that the following steps are included:
(1) in the presence of an organic, haloformate X3COOR2With alkenyl halide R1=CX1X2Preparation structure is reacted for raw material
Intermediate product (I) shown in formula (I)
Wherein:
R1Selected from-CH2、-CHCH3、-CF2、-CHCF3Or-CHCH2CF3；
R2Selected from-CH3、-CH2CH3、-CH2CH2CH3、-CH2CH2CH2CH3、-CH(CH3)CH3、-CH2CH(CH3)CH3、-CH(CH3)
CH2CH3、-CH2CH2CH2CH2CH3、-CH2CH2CH2CH2CH2CH3Or-CH2CH2(CH2CH3)CH2CH2CH2CH3；
X1、X2And X3Independently selected from F, Cl, Br, I, and X1、X2And X3It is not simultaneously F；
(2) in the presence of an organic, under the action of catalyst, intermediate product (I) reacts preparation structure formula with fluorination reagent
(II) containing the carboxylate of trifluoromethyl shown in,
The fluorination reagent in potassium fluoride, cesium fluoride, zinc fluoride, copper fluoride, lithium fluoride, sodium fluoride and hydrogen fluoride one
Kind, two or three of combination of the above；
The catalyst is selected from benzyltriethylammoinium chloride (TEBA)；
The reaction temperature of the step (1) is -10 DEG C~70 DEG C, and the reaction temperature of step (2) is -10 DEG C~100 DEG C.
2. the preparation method of the carboxylate described in accordance with the claim 1 containing trifluoromethyl, it is characterised in that described:
R1Selected from-CH2、-CHCH3、-CF2Or-CHCF3；
R2Selected from-CH3、-CH2CH3Or-CH2CH2CH3；
X1、X2And X3Independently selected from F or Cl.
3. the preparation method of the carboxylate described in accordance with the claim 1 containing trifluoromethyl, it is characterised in that the fluorination reagent
Selected from one of potassium fluoride, cesium fluoride, zinc fluoride and hydrogen fluoride, two or three of combination of the above.
4. the preparation method of the carboxylate described in accordance with the claim 1 containing trifluoromethyl, it is characterised in that the organic solvent
Selected from methylene chloride, chloroform, carbon tetrachloride, ethyl acetate, propyl acetate, butyl acetate, dimethyl carbonate, diethyl carbonate or
With one of petroleum ether, two or three of combination of the above.
5. the preparation method of the carboxylate described in accordance with the claim 1 containing trifluoromethyl, it is characterised in that the halogen formate
Ester X3COOR2With alkenyl halide R1=CX1X2Mol ratio be 1:1~1:9.
6. the preparation method of the carboxylate containing trifluoromethyl according to claim 5, it is characterised in that the halogen formate
Ester X3COOR2With alkenyl halide R1=CX1X2Mol ratio be 1:1~1:5.
7. the preparation method of the carboxylate described in accordance with the claim 1 containing trifluoromethyl, it is characterised in that the intermediate product
(I) it is 1:1~1:9 with the mol ratio of fluorination reagent, intermediate product (I) and the mol ratio of catalyst are 1:0.005~1:
0.05。
8. the preparation method of the carboxylate containing trifluoromethyl according to claim 7, it is characterised in that the intermediate product
(I) it is 1:1~1:5 with the mol ratio of fluorination reagent, intermediate product (I) and the mol ratio of catalyst are 1:0.005~1:
0.01。
9. the preparation method of the carboxylate described in accordance with the claim 1 containing trifluoromethyl, it is characterised in that the step (1)
Reaction temperature is -10 DEG C~40 DEG C, and the reaction temperature of step (2) is 0 DEG C~60 DEG C.
10. according to the preparation method of the carboxylate described in one of claim 1 to 9 containing trifluoromethyl, it is characterised in that described
Carboxylate containing trifluoromethyl is used for lithium-ion battery electrolytes.
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| CN109336734B (en) * | 2018-06-21 | 2022-03-25 | 苏州工业园区天意达新材料科技有限公司 | Ethyl perfluorohexyl acetic acid and synthesis method thereof |
| CN109301327B (en) * | 2018-09-29 | 2021-05-18 | 桑顿新能源科技有限公司 | Electrolyte and lithium ion battery |
| CN110903183A (en) * | 2019-12-20 | 2020-03-24 | 湖南有色郴州氟化学有限公司 | Novel preparation method of 3,3, 3-trifluoropropionic acid |
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|---|---|---|---|---|
| WO2007143154A1 (en) * | 2006-06-02 | 2007-12-13 | Purdue Research Foundation | Methods for preparing halohydrins and methods for preparing epoxides |
| CN102219684A (en) * | 2011-04-26 | 2011-10-19 | 巨化集团公司 | Preparation method of trifluoromethyl halogenated carboxylate |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007143154A1 (en) * | 2006-06-02 | 2007-12-13 | Purdue Research Foundation | Methods for preparing halohydrins and methods for preparing epoxides |
| CN102219684A (en) * | 2011-04-26 | 2011-10-19 | 巨化集团公司 | Preparation method of trifluoromethyl halogenated carboxylate |
Non-Patent Citations (2)
| Title |
|---|
| A convenient synthesis of ethyl 3,3,3-trifluoropropanoate and its 2-bromo derivative;Molines, H.等;《Journal of Fluorine Chemistry》;19871231;第37卷(第2期);第183-189页 * |
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