CN105348100A - Method for synthesizing fluoro ethyl acetate and fluoro methyl acetate - Google Patents
Method for synthesizing fluoro ethyl acetate and fluoro methyl acetate Download PDFInfo
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- CN105348100A CN105348100A CN201510909353.8A CN201510909353A CN105348100A CN 105348100 A CN105348100 A CN 105348100A CN 201510909353 A CN201510909353 A CN 201510909353A CN 105348100 A CN105348100 A CN 105348100A
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- chloroacetate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention provides a method for synthesizing fluoro ethyl acetate or fluoro methyl acetate. According to the method, chloro-alkyl imidazole ionic liquid and/or bromo-alkyl imidazole ionic liquid is taken as the catalyst, ethyl chloroacetate or ethyl chloroacetate and alkali metal fluorides are taken as raw materials, a polar aprotic solvent is taken as the reaction medium, filtration is conducted after reaction is conducted for a while at a set temperature to remove inorganic salt, and then fluoro ethyl acetate or fluoro methyl acetate is obtained.
Description
Technical field
The present invention relates to the synthetic method of a kind of fluoroacetic ethyl ester and fluoroacetic methyl esters, belong to the field of organic chemical industry's technology.
Background technology
Fluorine is the maximum element of electronegativity, introduces fluorine atom, often can give compound some special character in compound.Due to the high electronegativity of fluorine atom, the distribution of cloud density in molecule can be changed, be conducive to putting forward high molecular activity; The introducing of fluorine atom can not only strengthen the fat-soluble of compound, and the bond energy of formation C-F key is higher than c h bond, is conducive to hindering metabolic process, can stops insect, the growth of weeds; C-F bond polarity is lower, has larger hydrophobicity, and this makes it have a wide range of applications in textiles and tensio-active agent.
Ethyl fluoroacetate is the important chemical intermediate of a class, is the raw material synthesizing multiple pharmaceutical intermediate.In compound, introduce fluorine atom have many kinds of methods, mainly comprise direct fluorination, electrochemical fluorination, Balz-Schiemann fluorination method and halogen-exchange fluorination method.Halogen exchange method is current a kind of most widely used method.Halogen exchange method mainly refers to that the compound (halogen refers generally to chlorine or bromine) adopted containing halogen atom is with alkali-metal fluorochemical or the method for the quaternary amine generation nucleophilic substitution reaction of contain fluorine atoms, and this method has good position specific.
The reaction of halogen exchange reaction solid phase and liquid phase two-phase often, two phase molecules are difficult to pile up, the speed of impact reaction, in order to improve two alternate mass transfer abilities, increase intermolecular probability of collision, improve the speed of reaction, often need to add appropriate phase-transfer catalyst.In fluoridation, the phase-transfer catalyst of most study mainly contains three kinds at present: drone salt form, comprises quaternary ammonium salt and quaternary alkylphosphonium salt etc., polyoxyethylene glycol and crown ether-like.
PinakiS utilizes the character of the low melting point of quaternary ammonium salt; using quaternary ammonium salt as reaction medium; ethyl fluoroacetate is generated as raw material by there is halogen exchange reaction with Potassium monofluoride (KF) by ethyl chloroacetate or ethyl bromoacetate; obtain comparatively ideal productive rate; but need the amount of the quaternary ammonium salt used larger in this process; cost is higher, and reaction process needs to protect with nitrogen.
Potassium monofluoride (KF) and CaF2 mix by JunkoIchihara according to a certain percentage, and at 110 DEG C of reaction 48h, obtain the fluoroacetic ethyl ester of 75%, although the method can obtain good yield, the required reaction times is longer.
Li Li adopts Potassium monofluoride and methyl chloroacetate to react, and limit coronite is distilled, and obtains the methylfluoracetate of 65%.
Wang Shu adopts clearly Tetrabutyl amonium bromide to make catalyzer, and using ethyl chloroacetate and Potassium monofluoride (KF) as raw material, heating reflux reaction 8h, obtain the yield of 73.5%, the reaction times is long.
The present invention utilizes ionic liquid to have certain dissolving power to Potassium monofluoride and ethyl chloroacetate, it can be used as solvent and catalyzer to synthesize fluoroacetic ethyl ester and fluoroacetic methyl esters, achieves the productive rate more excellent than traditional quaternary ammonium salt catalyst.
Summary of the invention
The invention provides a kind of ionic liquid that adopts as catalyzer, the method for synthesizing fluoro ethyl acetate and fluoroacetic methyl esters.
The present invention is by the following aspects content:
1. the method for a synthesizing fluoro ethyl acetate or fluoroacetic methyl esters, it is characterized in that at chloro 1-methyl-3-alkyl imidazole type ionic liquid and/or bromo 1-methyl-3-alkyl imidazole type ionic liquid as under the condition of catalyzer, using ethyl chloroacetate or methyl chloroacetate and Potassium monofluoride as raw material, adding solvent, is 110 ~ 150 DEG C in temperature, after reaction 2 ~ 5h, be cooled to 10 ~ 30 DEG C, filter, filtrate is distilled, obtains ethyl fluoroacetate or methylfluoracetate.
2. the alkyl of chloro 1-methyl-3-alkyl imidazole type ionic liquid described in and/or bromo 1-methyl-3-alkyl imidazole type ionic liquid is the straight chain of C1 ~ C10 or the alkyl of side chain, and ionic liquid mole dosage is 1.5% ~ 4% of feed molar number.
3. Potassium monofluoride mole dosage described in is 1.1 ~ 2.5 times of ethyl chloroacetate or methyl chloroacetate mole number.
4. the solvent described in is aprotic, polar type solvent, and its Typical Representative is DMF, N,N-dimethylacetamide, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, 100 ~ 500 times that the volumetric usage (milliliter) of solvent is ethyl chloroacetate or methyl chloroacetate mole number.
Beneficial effect of the present invention:
1 process of the present invention is without the need to using nitrogen protection, and easy control of reaction conditions, is conducive to suitability for industrialized production.
2 chloros or bromo 1-methyl-3-alkyl imidazole type ionic liquid are in the present invention not only as solvent but also as catalyzer, and decrease the use of reagent, its effect is more excellent than traditional catalyzer.
The consumption of 3 catalyzer is few, just can obtain desirable productive rate in the short period of time.
Embodiment
To be further detailed the present invention by specific embodiment below, but concrete scope of the present invention is not
Be confined to embodiment.
Embodiment 1:
In the flask of 100ml, add 4.35g (0.075mol) Potassium monofluoride (KF), 20mlN, dinethylformamide, the ethyl chloroacetate of 6.125g (0.05mol), 0.219g (0.001mol) bromo 1-butyl-3-Methylimidazole, is warming up to 130 DEG C of reaction 3h.
After reaction terminates, be cooled to room temperature, filter, obtain the filtrate of black, get filtrate and carry out stratographic analysis, productive rate is 72.47%.
Embodiment 2:
In the flask of 100ml, add 4.35g (0.075mol) Potassium monofluoride (KF), 20mlN, dinethylformamide, the ethyl chloroacetate of 6.125g (0.05mol), 0.219g (0.001mol) bromo 1-butyl-3-Methylimidazole, is warming up to 130 DEG C of reaction 4h.
After reaction terminates, be cooled to room temperature, filter, obtain the filtrate of black, get filtrate and carry out stratographic analysis, productive rate is 75.46%.
Embodiment 3:
In the flask of 100ml, add 5.075g (0.0875mol) Potassium monofluoride (KF), 20mlN, dinethylformamide, the ethyl chloroacetate of 6.125g (0.05mol), 0.219g (0.001mol) bromo 1-butyl-3-Methylimidazole, is warming up to 130 DEG C of reaction 3h.
After reaction terminates, be cooled to room temperature, filter, obtain the filtrate of black, get filtrate and carry out stratographic analysis, productive rate is 74.09%.
Embodiment 4:
In the flask of 100ml, add 4.35g (0.075mol) Potassium monofluoride (KF), 20mlN, dinethylformamide, the ethyl chloroacetate of 6.125g (0.05mol), 0.219g (0.001mol) bromo 1-butyl-3-Methylimidazole, is warming up to 120 DEG C of reaction 4h.
After reaction terminates, be cooled to room temperature, filter, obtain the filtrate of black, get filtrate and carry out stratographic analysis, productive rate is 74.19%.
Embodiment 5:
In the flask of 100ml, add 5.075g (0.0875mol) Potassium monofluoride (KF), 20mlN, dinethylformamide, the ethyl chloroacetate of 6.125g (0.05mol), 0.1643g (0.00075mol) bromo 1-butyl-3-Methylimidazole, is warming up to 140 DEG C of reaction 3h.
After reaction terminates, be cooled to room temperature, filter, obtain the filtrate of black, get filtrate and carry out stratographic analysis, productive rate is 72.09%.
Embodiment 6:
In the flask of 100ml, add 4.35g (0.075mol) Potassium monofluoride (KF), 20mlN, dinethylformamide, the ethyl chloroacetate of 6.125g (0.05mol), 0.3210g (0.002mol) chloro 1-butyl-3-Methylimidazole, is warming up to 130 DEG C of reaction 4h.
After reaction terminates, be cooled to room temperature, filter, obtain the filtrate of black, get filtrate and carry out stratographic analysis, productive rate is 75.26%.
Claims (4)
1. the method for a synthesizing fluoro ethyl acetate or fluoroacetic methyl esters, it is characterized in that at chloro 1-methyl-3-alkyl imidazole type ionic liquid and/or bromo 1-methyl-3-alkyl imidazole type ionic liquid as under the condition of catalyzer, using ethyl chloroacetate or methyl chloroacetate and Potassium monofluoride as raw material, adding solvent, is 110 ~ 150 DEG C in temperature, after reaction 2 ~ 5h, be cooled to 10 ~ 30 DEG C, filter, filtrate is distilled, obtains ethyl fluoroacetate or methylfluoracetate.
2. method according to claim 1, it is characterized in that: the alkyl of described chloro 1-methyl-3-alkyl imidazole type ionic liquid and/or bromo 1-methyl-3-alkyl imidazole type ionic liquid is the straight chain of C1 ~ C10 or the alkyl of side chain, and ionic liquid mole dosage is 1.5% ~ 4% of feed molar number.
3. method according to claim 1, is characterized in that: described Potassium monofluoride mole dosage is 1.1 ~ 2.5 times of ethyl chloroacetate or methyl chloroacetate mole number.
4. method according to claim 1, it is characterized in that, described solvent is aprotic, polar type solvent, its Typical Representative is DMF, N, N-N,N-DIMETHYLACETAMIDE, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone, 100 ~ 500 times that the volumetric usage (milliliter) of solvent is ethyl chloroacetate or methyl chloroacetate mole number.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510909353.8A CN105348100A (en) | 2015-12-04 | 2015-12-04 | Method for synthesizing fluoro ethyl acetate and fluoro methyl acetate |
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| CN201510909353.8A CN105348100A (en) | 2015-12-04 | 2015-12-04 | Method for synthesizing fluoro ethyl acetate and fluoro methyl acetate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920644A (en) * | 2022-06-06 | 2022-08-19 | 福建省龙德新能源有限公司 | Method for synthesizing ethyl fluoroacetate by using double catalysts |
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- 2015-12-04 CN CN201510909353.8A patent/CN105348100A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114920644A (en) * | 2022-06-06 | 2022-08-19 | 福建省龙德新能源有限公司 | Method for synthesizing ethyl fluoroacetate by using double catalysts |
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