CN105037150A - 2-fluoropropionate synthetizing method - Google Patents

2-fluoropropionate synthetizing method Download PDF

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CN105037150A
CN105037150A CN201510435286.0A CN201510435286A CN105037150A CN 105037150 A CN105037150 A CN 105037150A CN 201510435286 A CN201510435286 A CN 201510435286A CN 105037150 A CN105037150 A CN 105037150A
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general formula
ester
reaction
synthetic method
chxcoor
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CN105037150B (en
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叶立峰
王树华
余燕
汪宇轩
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Juhua Group Corp
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Juhua Group Technology Centre
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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

Abstract

The invention discloses a 2-fluoropropionate synthetizing method. The method comprise the steps of 1, adding ester to a four-mouth flask provided with a condenser pipe, wherein the general formula of the ester is CH3CHXCOOR, and R represents alkyl; 2, adding an addition agent, a catalyst and solvent to the four-mouth flask, and then adding a fluorinated reagent and conducting stirring to obtain reaction liquid; 3, heating the reaction liquid to a set temperature, wherein reaction time is 3-16 h; 4, conducting rectification after reaction ends to obtain a 2-fluoropropionate target product. According to the method, cheap 2-CH3CHClCOOR is used as the raw material, and fluorination is conducted with potassium fluoride in the presence of the addition agent to obtain the 2-fluoropropionate. The method has the advantages that the reaction condition is mild, the yield is high, and cost is low. Due to the fact that the addition agent is added, generation of high-boiling by-products can be restrained, and then reaction selectivity is improved.

Description

A kind of synthetic method of 2-fluorine propionic ester
Technical field
The present invention relates to a kind of preparation method of fluoroalkyl, particularly relate to a kind of synthetic method of 2-fluorine propionic ester.
Background technology
Poly-2-fluorinated monomer has the advantages such as second-order transition temperature is high, surface energy is low, ageing-resistant, signal attenuation is low, can be used in plastic optical fiber, and 2-fluorine propionic ester is the key intermediate of synthesis 2-fluorinated monomer.The synthesis of 2-fluorine propionic ester mainly contains three routes.(1) with 2-chloropropionate for raw material.According to RecuildestrvauxdesPays-BasdesPays-Bas; (1947); P.424 report under 180 ~ 190 DEG C of conditions, 2-chloropropionate and Potassium monofluoride carry out fluorine chlorine and exchange to obtain 2-fluorine propionic ester, yield 56%.CN103044245A reports, 2-chloropropionate and liquid-fluorination hydrogen carry out exchange chloride for fluoride and obtains 2-fluorine propionic ester, the highest yield 83% under catalyst.(2) with 2 bromopropionic acid ester for starting raw material, JournalofFluorineChemisty; Vol.99; Nb.2; (1999) report, under the catalysis of tributyl hexadecyl bromo-phosphonium, Potassium monofluoride and 2 bromopropionic acid ethyl ester react 60, obtain 2-fluorine ethyl propionate, yield 80%.(3) with 2 hydroxy propanoic acid ester for raw material, ChemicalCommunications; Nb.2; (1999); P.215-216 reporting, take methylene dichloride as solvent, and 2 hydroxy propanoic acid ester and two (2-methoxyl group) amino sulfur trifluoride react to obtain 2-fluorine ethyl propionate at 25 DEG C, yield 73%.
The method of the above-mentioned various 2-of preparation fluorine propionic ester all has certain weak point.2-chloropropionate is that raw materials cost is low, but it is low to fluoridize yield with Potassium monofluoride, and temperature of reaction is high, causes a large amount of three wastes; Fluoridize dangerous large with hydrogen fluoride, equipment corrosion is serious, spent catalyst difficult treatment.With 2 bromopropionic acid ester for raw material process route cost of material is high, cost is high; The operational path being raw material with 2 hydroxy propanoic acid ester has the deficiencies such as fluorination reagent is expensive, operation is very dangerous.
Summary of the invention
The present invention is directed to the deficiencies in the prior art part, a kind of synthetic method of 2-fluorine propionic ester is provided, with the 2-chloropropionate (CH of cheapness 3cHClCOOR) be raw material, under auxiliary agent existent condition, fluoridize the technique obtaining 2-fluorine propionic ester with Potassium monofluoride, auxiliary agent add the generation that can suppress the high by product that boils, thus improve the selectivity of reaction, the general formula adopting this technique to prepare is (CH 3cHFCOOR) 2-fluorine propionic ester has reaction conditions gentleness, and yield is high, the advantage that cost is low.
In order to solve the problems of the technologies described above, the present invention adopts following technical scheme:
A synthetic method for 2-fluorine propionic ester, is characterized in that comprising the steps:
1) first in a four-hole boiling flask with prolong, adding general formula is CH 3the ester of CHXCOOR, wherein R represents alkyl;
2) then in four-hole boiling flask, add auxiliary agent, catalysts and solvents, then add fluorination reagent and carry out stirring and obtain reaction solution;
3) above-mentioned reaction solution is heated to design temperature, the reaction times is 3 ~ 16h;
4), after reaction terminates, carry out rectifying, obtain 2-fluorine propionic ester target product.
Preferably, general formula is CH 3x in the ester of CHXCOOR represents halogen, and halogen is Cl.
Preferably, fluorination reagent is Potassium monofluoride, and fluorination reagent and general formula are CH 3the mol ratio of the ester of CHXCOOR is 1.0 ~ 2.5:1, and the price of Potassium monofluoride is low, reduces manufacturing cost, and mol ratio is low, then reaction yield is low, and mol ratio is high, then reaction yield is high, but fluorination reagent and CH 3the mol ratio of the ester of CHXCOOR exceedes to a certain degree, then yield improves not obvious, simultaneously also uneconomical.
Further, auxiliary agent is general formula is R 1c (OR 2) 3compound, R 1for H or CH 3in one, R 2for CH 3or C 2h 5in one, general formula is R 1c (OR 2) 3compound and general formula be CH 3the mass ratio of the ester of CHXCOOR is 0.02 ~ 0.2:1, and auxiliary agent can reduce high-boiling-point impurity and generate, and can improve selectivity and the yield of reaction simultaneously.
Further, catalyzer is phase-transfer catalyst, comprises quaternary ammonium salt, quaternary alkylphosphonium salt, crown ether, and catalyzer and general formula are CH 3the mass ratio of the ester of CHXCOOR is 0.05 ~ 0.3:1.
Preferably, quaternary ammonium salt is one or more mixtures in Dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, tetrabutylammonium chloride and Tetrabutyl amonium bromide, and quaternary alkylphosphonium salt is Tetraphenylphosphonium Bromide, and crown ether is 18-hat-6 or 15-hat-5.
Further, solvent is polar solvent, comprises tetramethylene sulfone, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone and DMF, and solvent and general formula are CH 3the mass ratio of the ester of CHXCOOR is 2 ~ 10:1, and solvent load is few, and reaction system solid content is large, and stir difficulty, be unfavorable for that reaction is carried out, solvent load is excessive, then speed of response is slow, simultaneously also uneconomical.
Further, design temperature is 80 ~ 160 DEG C, and temperature of reaction is low, then speed of response is slow, long reaction time, and temperature of reaction is high, then side reaction increases, and yield is lower.
The present invention, owing to have employed technique scheme, has following beneficial effect:
1, the general formula adopting this technique to prepare is (CH 3cHFCOOR) 2-fluorine propionic ester has reaction conditions gentleness, and yield is high, the advantage that cost is low;
2, with the 2-chloropropionate (CH of cheapness 3cHClCOOR) be raw material, under auxiliary agent existent condition, fluoridize the technique obtaining 2-fluorine propionic ester with Potassium monofluoride, auxiliary agent add the generation that can suppress the high by product that boils, thus improve the selectivity of reaction.
Embodiment
The invention provides a kind of synthetic method of 2-fluorine propionic ester, comprise the steps:
1) first in a four-hole boiling flask with prolong, adding general formula is CH 3the ester of CHXCOOR, wherein R represents alkyl, and alkyl comprises halogen-containing alkyl and not halogen-containing alkyl and halogen-containing aromatic ring yl and not halogen-containing aromatic ring yl, as methyl, ethyl, 2,2,2-trifluoroethyl (CF 3cH 2), phenyl, rubigan, pentafluorophenyl group etc., preferably, general formula is CH 3x in the ester of CHXCOOR represents halogen, and halogen is Cl;
2) then in four-hole boiling flask, add auxiliary agent, catalysts and solvents, auxiliary agent is general formula is R 1c (OR 2) 3compound, R 1for H or CH 3in one, R 2for CH 3or C 2h 5in one, general formula is R 1c (OR 2) 3compound and general formula be CH 3the mass ratio of the ester of CHXCOOR is 0.02 ~ 0.2:1, and auxiliary agent can reduce high-boiling-point impurity and generate, and can reduce selectivity and the yield of reaction, catalyzer is phase-transfer catalyst, comprises quaternary ammonium salt, quaternary alkylphosphonium salt, crown ether, and catalyzer and general formula are CH simultaneously 3the mass ratio of the ester of CHXCOOR is 0.05 ~ 0.3:1, preferably, quaternary ammonium salt is one or more mixtures in Dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, tetrabutylammonium chloride and Tetrabutyl amonium bromide, quaternary alkylphosphonium salt is Tetraphenylphosphonium Bromide, crown ether is 18-hat-6 or 15-hat-5, solvent is polar solvent, comprises tetramethylene sulfone, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone and DMF, and solvent and general formula are CH 3the mass ratio of the ester of CHXCOOR is 2 ~ 10:1, solvent load is few, and reaction system solid content is large, stirs difficulty, be unfavorable for that reaction is carried out, solvent load is excessive, then speed of response is slow, simultaneously also uneconomical, add fluorination reagent again to carry out stirring and obtain reaction solution, preferably, fluorination reagent is Potassium monofluoride, and fluorination reagent and general formula are CH 3the mol ratio of the ester of CHXCOOR is 1.0 ~ 2.5:1, and the price of Potassium monofluoride is low, reduces manufacturing cost, and mol ratio is low, then reaction yield is low, and mol ratio is high, then reaction yield is high, but fluorination reagent and CH 3the mol ratio of the ester of CHXCOOR exceedes to a certain degree, then yield improves not obvious, simultaneously also uneconomical;
3) above-mentioned reaction solution is heated to design temperature, design temperature is 80 ~ 160 DEG C, and temperature of reaction is low, then speed of response is slow, long reaction time, and temperature of reaction is high, then side reaction increases, and yield is lower, and the reaction times is 3 ~ 16h;
4), after reaction terminates, carry out rectifying, obtain 2-fluorine propionic ester target product.
Embodiment 1
In a 2L four-hole boiling flask with prolong, add tetramethylene sulfone 720g, 2-methyl chloropropionate 245g (2.0mol), Dodecyl trimethyl ammonium chloride 25g, trimethyl orthoacetate 25g, Potassium monofluoride 220.1g, stir, be warming up to 120 DEG C, reaction 6h.After reaction terminates, reaction solution rectifying, obtains 2-fluorine methyl propionate 150g, purity 99.2%; Yield 70.2%.
Embodiment 2
In a 2L four-hole boiling flask with prolong, add DMF1100g, 2-chloropropionate 273g (2.0mol), Tetrabutyl amonium bromide 54g, triethyl orthoformate 5.5g, Potassium monofluoride 255.2g, stir, be warming up to 100 DEG C, reaction 12h.After reaction terminates, rectifying, obtains 2-fluorine ethyl propionate 176.3g, purity 99.5%; Yield 66.5%.
Embodiment 3
Dimethyl sulfoxide (DMSO) 1650g, 2-chloropropionic acid pentafluorophenyl group ester 274.5g (1.0mol), Tetraphenylphosphonium Bromide 83g, trimethyl orthoacetate 17g is added in a 3L four-hole boiling flask with prolong, Potassium monofluoride 92.8g, stir, be warming up to 140 DEG C, reaction 5h.After reaction terminates, rectifying, obtains 2-fluorine propionic acid pentafluorophenyl group ester 178.5g, purity 99.3%; Yield 68.7%.
Embodiment 4
In the 3L four-hole boiling flask of a band prolong, add methyl-2-pyrrolidone 1500g, 2-chloropropionic acid trifluoroethyl ester 190g (1.0mol), 18-is preced with-647g, triethly orthoacetate 25g, Potassium monofluoride 75.4g, stir, be warming up to 160 DEG C, reaction 3h.After reaction terminates, rectifying, obtains 2-fluorine propionic acid trifluoroethyl ester 114g, purity 99.6%; Yield 65.2%.
Embodiment 5
Tetramethylene sulfone 440g, 2-chloropropionic acid rubigan ester 219g (1.0mol), octadecyl trimethyl ammonium chloride 33g, trimethyl orthoformate 35g is added in a 2L four-hole boiling flask with prolong, Potassium monofluoride 145g, stir, be warming up to 80 DEG C, reaction 16h.After reaction terminates, rectifying, obtains 2-fluorine propionic acid rubigan ester 132g, purity 99.0%; Yield 64.5%.
Embodiment 6
In a 3L four-hole boiling flask with prolong, add DMF1800g, 2-chloropropionic acid phenylester 184.5g (1.0mol), benzyl trimethyl ammonium chloride 9g, trimethyl orthoacetate 37g, Potassium monofluoride 58g, stir, be warming up to 110 DEG C, reaction 9h.After reaction terminates, rectifying, obtains 2-fluorine propionic acid phenylester 106g, purity 99.1%; Yield 62.5%.
Comparative example 1
In a 2L four-hole boiling flask with prolong, add tetramethylene sulfone 720g, 2-methyl chloropropionate 245g (2.0mol), Dodecyl trimethyl ammonium chloride 25g, Potassium monofluoride 220.1g, stir, be warming up to 120 DEG C, reaction 6h.After reaction terminates, reaction solution rectifying, obtains 2-fluorine methyl propionate 117.5g, purity 99.2%; Yield 55%.
These are only specific embodiments of the invention, but technical characteristic of the present invention is not limited thereto.Any based on the present invention, for realizing substantially identical technique effect, done ground simple change, equivalent replacement or modification etc., be all covered by among protection scope of the present invention.

Claims (8)

1. a synthetic method for 2-fluorine propionic ester, is characterized in that comprising the steps:
1) first in a four-hole boiling flask with prolong, adding general formula is CH 3the ester of CHXCOOR, wherein R represents alkyl;
2) then in described four-hole boiling flask, add auxiliary agent, catalysts and solvents, then add fluorination reagent and carry out stirring and obtain reaction solution;
3) above-mentioned reaction solution is heated to design temperature, the reaction times is 3 ~ 16h;
4), after reaction terminates, carry out rectifying, obtain 2-fluorine propionic ester target product.
2. the synthetic method of a kind of 2-fluorine propionic ester according to claim 1, is characterized in that: described general formula is CH 3x in the ester of CHXCOOR represents halogen, and described halogen is Cl.
3. the synthetic method of a kind of 2-fluorine propionic ester according to claim 1, it is characterized in that: described fluorination reagent is Potassium monofluoride, described fluorination reagent and described general formula are CH 3the mol ratio of the ester of CHXCOOR is 1.0 ~ 2.5:1.
4. the synthetic method of a kind of 2-fluorine propionic ester according to claim 1, is characterized in that: described auxiliary agent is general formula is R 1c (OR 2) 3compound, R 1for H or CH 3in one, R 2for CH 3or C 2h 5in one, described general formula is R 1c (OR 2) 3compound and described general formula be CH 3the mass ratio of the ester of CHXCOOR is 0.02 ~ 0.2:1.
5. the synthetic method of a kind of 2-fluorine propionic ester according to claim 1, it is characterized in that: described catalyzer is phase-transfer catalyst, comprise quaternary ammonium salt, quaternary alkylphosphonium salt, crown ether, described catalyzer and described general formula are CH 3the mass ratio of the ester of CHXCOOR is 0.05 ~ 0.3:1.
6. the synthetic method of a kind of 2-fluorine propionic ester according to claim 5, it is characterized in that: described quaternary ammonium salt is one or more mixtures in Dodecyl trimethyl ammonium chloride, octadecyl trimethyl ammonium chloride, tetrabutylammonium chloride and Tetrabutyl amonium bromide, described quaternary alkylphosphonium salt is Tetraphenylphosphonium Bromide, and described crown ether is 18-hat-6 or 15-hat-5.
7. the synthetic method of a kind of 2-fluorine propionic ester according to claim 1, it is characterized in that: described solvent is polar solvent, comprise tetramethylene sulfone, dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone and DMF, described solvent and described general formula are CH 3the mass ratio of the ester of CHXCOOR is 2 ~ 10:1.
8. the synthetic method of a kind of 2-fluorine propionic ester according to claim 1, is characterized in that: described design temperature is 80 ~ 160 DEG C.
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Cited By (1)

* Cited by examiner, † Cited by third party
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

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020059187A1 (en) * 1998-09-21 2002-05-16 Microsoft Corporation Internal database validation
CN101528662A (en) * 2006-10-27 2009-09-09 拜尔作物科学股份公司 Stereoselective one step fluorination process for the preparation of 2-fluoropropionate
CN103044245A (en) * 2012-12-12 2013-04-17 巨化集团技术中心 Method for preparing 2-fluoropropionate
CN103159626A (en) * 2011-12-14 2013-06-19 中化蓝天集团有限公司 Method for preparing 3- fluoropropionate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20020059187A1 (en) * 1998-09-21 2002-05-16 Microsoft Corporation Internal database validation
CN101528662A (en) * 2006-10-27 2009-09-09 拜尔作物科学股份公司 Stereoselective one step fluorination process for the preparation of 2-fluoropropionate
CN103159626A (en) * 2011-12-14 2013-06-19 中化蓝天集团有限公司 Method for preparing 3- fluoropropionate
CN103044245A (en) * 2012-12-12 2013-04-17 巨化集团技术中心 Method for preparing 2-fluoropropionate

Cited By (1)

* Cited by examiner, † Cited by third party
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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