CN114057562A - Preparation method of 4,4, 4-trifluorobutyric acid - Google Patents
Preparation method of 4,4, 4-trifluorobutyric acid Download PDFInfo
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- CN114057562A CN114057562A CN202111480222.4A CN202111480222A CN114057562A CN 114057562 A CN114057562 A CN 114057562A CN 202111480222 A CN202111480222 A CN 202111480222A CN 114057562 A CN114057562 A CN 114057562A
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- WTUCTMYLCMVYEX-UHFFFAOYSA-N 4,4,4-trifluorobutanoic acid Chemical compound OC(=O)CCC(F)(F)F WTUCTMYLCMVYEX-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 31
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 31
- 239000007818 Grignard reagent Substances 0.000 claims abstract description 20
- 150000004795 grignard reagents Chemical class 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 44
- 239000000243 solution Substances 0.000 claims description 40
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 22
- 238000010992 reflux Methods 0.000 claims description 14
- 238000006460 hydrolysis reaction Methods 0.000 claims description 12
- 239000002798 polar solvent Substances 0.000 claims description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- ZPIFKCVYZBVZIV-UHFFFAOYSA-N 3-chloro-1,1,1-trifluoropropane Chemical compound FC(F)(F)CCCl ZPIFKCVYZBVZIV-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 abstract description 6
- 239000011737 fluorine Substances 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 238000003747 Grignard reaction Methods 0.000 abstract description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 11
- ZUXGOABWWUCPQR-UHFFFAOYSA-M [Cl-].FC(F)(F)CC[Mg+] Chemical compound [Cl-].FC(F)(F)CC[Mg+] ZUXGOABWWUCPQR-UHFFFAOYSA-M 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- FDMFUZHCIRHGRG-UHFFFAOYSA-N 3,3,3-trifluoroprop-1-ene Chemical compound FC(F)(F)C=C FDMFUZHCIRHGRG-UHFFFAOYSA-N 0.000 description 1
- SAUGMJLWYLQPEM-UHFFFAOYSA-N 3-bromo-1,1,1-trifluoropropane Chemical compound FC(F)(F)CCBr SAUGMJLWYLQPEM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/15—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction of organic compounds with carbon dioxide, e.g. Kolbe-Schmitt synthesis
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a synthetic method of fluoroalkyl acid, in particular to a preparation method of 4,4, 4-trifluorobutyric acid, belonging to the technical field of organic fluorine chemical industry. The invention relates to a preparation method of 4,4, 4-trifluorobutyric acid, which uses Grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide, and hydrolyzing under acidic condition to obtain 4,4, 4-trifluorobutyric acid. The Grignard reaction method is adopted, the reaction can be carried out under normal pressure or low pressure and common temperature, the reaction condition is mild, the reaction time is short, and byproducts are easy to separate. The preparation method of the 4,4, 4-trifluorobutyric acid has the advantages of simple and easy reaction process, high conversion rate of more than 83 percent, less byproducts, recyclable solvent, safety, environmental protection, continuous feeding and easy realization of large-scale industrial co-production.
Description
Technical Field
The invention relates to a synthetic method of fluoroalkyl acid, in particular to a preparation method of 4,4, 4-trifluorobutyric acid, belonging to the technical field of organic fluorine chemical industry.
Background
4,4, 4-trifluorobutyric acid (TFBA) is an important intermediate of a medicine synthetic material and an organic fluorine material. Mainly used for combiningInto functional polymer material and fine chemical containing fluorine. Such as fluorine-containing surfactant, fluorine grease and the like, and has wide application prospect. The pure TFBA is colorless and transparent acidic liquid with pungent smell, is very easy to absorb water and decompose in the air, and has strong corrosivity. Molecular formula C of TFBA4H5F3O2The relative molecular mass is 142.1, the boiling point is 166-167 ℃, the melting point is 30 ℃, and the relative density of liquid is 1.4.
The synthesis method of 4,4, 4-trifluorobutyric acid in the prior art mainly comprises the following synthesis routes: the first method adopts 1-iodine-3, 3, 3-trifluoropropane as a raw material; the second method adopts 3,3, 3-trifluoropropene and carbon monoxide as raw materials; the third method adopts 3-bromo-1, 1, 1-trifluoropropane and carbon dioxide as raw materials; the fourth method adopts carbon tetrachloride and butyric acid as raw materials. The acidic waste water generated by the reaction is more, which is not beneficial to environmental protection; the catalyst has large dosage and high cost; long reaction process, low product yield and the like.
In order to solve the problems in the preparation of 4,4, 4-trifluorobutyric acid in the prior art, the invention provides a novel preparation method.
Disclosure of Invention
In order to overcome the technical defects of environmental protection inconvenience, large using amount of catalyst, high cost, longer reaction process, lower product yield and the like in the preparation of 4,4, 4-trifluorobutyric acid in the prior art, the invention provides a preparation method of 4,4, 4-trifluorobutyric acid, and the preparation method of 4,4, 4-trifluorobutyric acid adopts a Grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide, and hydrolyzing under acidic condition to obtain 4,4, 4-trifluorobutyric acid. The reaction can be carried out under normal pressure or low pressure and common temperature, the reaction condition is mild, the reaction time is short, and byproducts are easy to separate.
In order to achieve the above object, the technical solution adopted by the present invention to solve the technical problem is a method for preparing 4,4, 4-trifluorobutyric acid, comprising the following steps:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide: dissolving carbon dioxide in polar solvent, and dripping into the prepared Grignard reagent CF3CH2CH2Stirring and refluxing the MgCl mixed solution at the temperature of 0-80 ℃ for 1-6 h to react to obtain CF3CH2CH2COOMgCl, the reaction equation of which is as follows:
(2) And (3) hydrolysis reaction: CF (compact flash)3CH2CH2COOMgCl is hydrolyzed under acidic conditions to generate 4,4, 4-trifluorobutyric acid, and the reaction equation is as follows:
preferably, the Grignard reagent CF3CH2CH2MgCl is prepared by synthesizing raw materials of trifluoro-chloropropane and magnesium metal.
Preferably, the polar solvent in step (1) is one or more of diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, toluene, N-methylmorpholine, N-dimethylaniline and pyridine.
Preferably, the polar solvent in step (1) is tetrahydrofuran.
Preferably, the dosage of the polar solvent in the step (1) is 0.5-5 times of the dosage of the carbon dioxide.
Preferably, the dosage of the polar solvent in the step (1) is 0.8-1.2 times of the dosage of the carbon dioxide.
Preferably, the reaction conditions in the step (1) are that the reaction temperature is 30-70 ℃ and the reflux reaction time is 1-5 h.
The acid in the acidic condition in the step (2) is one or more of hydrochloric acid, sulfuric acid and nitric acid.
Preferably, the acid in the acidic condition described in step (2) is hydrochloric acid.
The invention has the beneficial technical effects that:
1. the invention relates to a preparation method of 4,4, 4-trifluorobutyric acid, which uses Grignard reagent CF3CH2CH2MgCl and carbon dioxideAnd (3) reacting, and hydrolyzing under an acidic condition to obtain the 4,4, 4-trifluorobutyric acid. The Grignard reaction method is adopted, the reaction can be carried out under normal pressure or low pressure and common temperature, the reaction condition is mild, the reaction time is short, and byproducts are easy to separate.
2. The preparation method of the 4,4, 4-trifluorobutyric acid has the advantages of simple and easy reaction process, high conversion rate (the yield is more than 83 percent), less byproducts, recyclable solvent, safety, environmental protection, continuous feeding and easy realization of large-scale industrial co-production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention.
Example 1:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 66.0g (1.5 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 50 ℃, stirring and refluxing for 2h under 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2And adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
Example 2:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 66.0g (1.5 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 60 ℃, stirring and refluxing for reaction for 3 hours under the pressure of 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2And adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
Example 3:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 66.0g (1.5 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 40 ℃, stirring and refluxing for reaction for 4 hours under the pressure of 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2And adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
Example 4:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 59.4g (1.35 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 50 ℃, stirring and refluxing for reaction for 3 hours under the pressure of 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2Adding hydrochloric acid solution into COOMgCl solution, and stirringStirring and reacting for a certain time, and hydrolyzing to obtain the 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
Example 5:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 59.4g (1.35 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 60 ℃, stirring and refluxing for reaction for 4 hours under the pressure of 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2And adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
Example 6:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 59.4g (1.35 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 40 ℃, stirring and refluxing for 2h under 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2And adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
Example 7:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 72.60g (1.65 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 50 ℃, stirring and refluxing for reaction for 4 hours under the pressure of 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2And adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
Example 8:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 72.60g (1.65 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 60 ℃, stirring and refluxing for 2h under 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2And adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
Example 9:
(1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide:
to the dried reaction vessel, 1000mL (1.5 mol) of a 1.5mol/L tetrahydrofuran solution of trifluoropropylmagnesium chloride was added with stirring, and then a mixture of 72.60g (1.65 mol) of carbon dioxide and 250mL of tetrahydrofuran was added dropwise. After dripping, slowly heating to 40 ℃, stirring and refluxing for reaction for 3 hours under the pressure of 0-0.2 MPa, and reacting to obtain CF3CH2CH2COOMgCl solution.
(2) And (3) hydrolysis reaction:
to CF3CH2And adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid.
(3) After the reaction is finished, the product is extracted and separated by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, and the yield is weighed, detected and calculated, and the result is shown in table 1.
It should be noted that the above-mentioned preferred embodiments are merely illustrative of the technical concepts and features of the present invention, and are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A preparation method of 4,4, 4-trifluorobutyric acid is characterized by comprising the following steps:
1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide: dissolving carbon dioxide in polar solvent, and dripping into the prepared Grignard reagent CF3CH2CH2Stirring and refluxing the MgCl mixed solution at the temperature of 0-80 ℃ for 1-6 h to react to obtain CF3CH2CH2COOMgCl, the reaction equation of which is as follows:
2) and (3) hydrolysis reaction: CF (compact flash)3CH2CH2COOMgCl is hydrolyzed under acidic conditions to generate 4,4, 4-trifluorobutyric acid, and the reaction equation is as follows:
2. a process for the preparation of 4,4, 4-trifluorobutanoic acid according to claim 1, wherein: the Grignard reagent CF3CH2CH2MgCl is prepared by synthesizing raw materials of trifluoro-chloropropane and magnesium metal.
3. A process for the preparation of 4,4, 4-trifluorobutanoic acid according to claim 1, wherein: the polar solvent in the step 1) is one or more of diethyl ether, tetrahydrofuran, methyl tetrahydrofuran, toluene, N-methylmorpholine, N-dimethylaniline and pyridine.
4. A process for the preparation of 4,4, 4-trifluorobutanoic acid according to claim 3, wherein: the polar solvent in the step 1) is tetrahydrofuran.
5. A process for the preparation of 4,4, 4-trifluorobutanoic acid according to claim 1, wherein: the dosage of the polar solvent in the step 1) is 0.5-5 times of the dosage of the carbon dioxide.
6. A process for the preparation of 4,4, 4-trifluorobutanoic acid according to claim 5, wherein: the dosage of the polar solvent in the step 1) is 0.8-1.2 times of that of the carbon dioxide.
7. A process for the preparation of 4,4, 4-trifluorobutanoic acid according to claim 1, wherein: the reaction conditions in the step 1) are that the reaction temperature is 30-70 ℃ and the reflux reaction time is 1-5 h.
8. A process for the preparation of 4,4, 4-trifluorobutanoic acid according to claim 1, wherein: the acid in the acidic condition in the step 2) is one or more of hydrochloric acid, sulfuric acid and nitric acid.
9. A process for the preparation of 4,4, 4-trifluorobutanoic acid according to claim 8, wherein: the acid in the acidic condition in step 2) is hydrochloric acid.
10. A process for the preparation of 4,4, 4-trifluorobutanoic acid according to any one of claims 1 to 9, characterized by comprising the steps of:
1) grignard reagent CF3CH2CH2Reacting MgCl with carbon dioxide: dissolving carbon dioxide in polar solvent, and dripping into the prepared Grignard reagent CF by using a constant pressure dropping funnel3CH2CH2Stirring and refluxing the MgCl mixed solution at 40-60 ℃ for 2-4 h to obtain CF3CH2CH2CO0MgCl solution;
2) and (3) hydrolysis reaction: to CF3CH2CH2Adding a hydrochloric acid solution into the COOMgCl solution, stirring and reacting for a certain time, and hydrolyzing to obtain 4,4, 4-trifluorobutyric acid;
3) and after the reaction is finished, extracting and separating the product by dichloromethane to obtain 4,4, 4-trifluorobutyric acid, weighing, detecting and calculating the yield.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823952A (en) * | 2010-04-23 | 2010-09-08 | 大连理工大学 | Method for preparing 2,4,5-trifluorophenylacetic acid |
| CN109608324A (en) * | 2019-01-16 | 2019-04-12 | 成家钢 | A kind of preparation process of 2,2-dimethylbutyric acid |
| CN111454145A (en) * | 2020-05-13 | 2020-07-28 | 张明 | Preparation method of p-bromomethyl isophenylpropionic acid |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101823952A (en) * | 2010-04-23 | 2010-09-08 | 大连理工大学 | Method for preparing 2,4,5-trifluorophenylacetic acid |
| CN109608324A (en) * | 2019-01-16 | 2019-04-12 | 成家钢 | A kind of preparation process of 2,2-dimethylbutyric acid |
| CN111454145A (en) * | 2020-05-13 | 2020-07-28 | 张明 | Preparation method of p-bromomethyl isophenylpropionic acid |
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