CN116751122A - Method for preparing 4, 4-trifluoro butyric acid - Google Patents
Method for preparing 4, 4-trifluoro butyric acid Download PDFInfo
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- CN116751122A CN116751122A CN202310718682.9A CN202310718682A CN116751122A CN 116751122 A CN116751122 A CN 116751122A CN 202310718682 A CN202310718682 A CN 202310718682A CN 116751122 A CN116751122 A CN 116751122A
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- 238000000034 method Methods 0.000 title claims abstract description 26
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 title description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- ONDSBJMLAHVLMI-UHFFFAOYSA-N trimethylsilyldiazomethane Chemical compound C[Si](C)(C)[CH-][N+]#N ONDSBJMLAHVLMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- VOSQLWCTKGQTAY-UHFFFAOYSA-N 3,3,3-trifluoropropanoyl chloride Chemical compound FC(F)(F)CC(Cl)=O VOSQLWCTKGQTAY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims description 36
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 20
- 229910001923 silver oxide Inorganic materials 0.000 claims description 18
- 239000011787 zinc oxide Substances 0.000 claims description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052731 fluorine Inorganic materials 0.000 abstract description 5
- 239000011737 fluorine Substances 0.000 abstract description 5
- 239000012847 fine chemical Substances 0.000 abstract description 3
- FNAWJOBKLWLHTA-UHFFFAOYSA-N [4-(trifluoromethyl)benzoyl] 4-(trifluoromethyl)benzoate Chemical compound C1=CC(C(F)(F)F)=CC=C1C(=O)OC(=O)C1=CC=C(C(F)(F)F)C=C1 FNAWJOBKLWLHTA-UHFFFAOYSA-N 0.000 abstract 2
- 238000005580 one pot reaction Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 19
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 9
- JGKPBAFQXDHRCH-UHFFFAOYSA-N diazomethane;hexane Chemical compound C=[N+]=[N-].CCCCCC JGKPBAFQXDHRCH-UHFFFAOYSA-N 0.000 description 9
- 239000000758 substrate Substances 0.000 description 9
- WTUCTMYLCMVYEX-UHFFFAOYSA-N 4,4,4-trifluorobutanoic acid Chemical compound OC(=O)CCC(F)(F)F WTUCTMYLCMVYEX-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010907 mechanical stirring Methods 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- FFTOUVYEKNGDCM-OWOJBTEDSA-N (e)-1,3,3-trifluoroprop-1-ene Chemical compound F\C=C\C(F)F FFTOUVYEKNGDCM-OWOJBTEDSA-N 0.000 description 1
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 238000005684 Liebig rearrangement reaction Methods 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- ZUXGOABWWUCPQR-UHFFFAOYSA-M [Cl-].FC(F)(F)CC[Mg+] Chemical compound [Cl-].FC(F)(F)CC[Mg+] ZUXGOABWWUCPQR-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003339 best practice Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- ZKRJCMKLCDWROR-UHFFFAOYSA-N ethyl 4,4,4-trifluorobut-2-enoate Chemical compound CCOC(=O)C=CC(F)(F)F ZKRJCMKLCDWROR-UHFFFAOYSA-N 0.000 description 1
- PSRZMXNNQTWAGB-UHFFFAOYSA-N ethyl 4,4,4-trifluorobutanoate Chemical compound CCOC(=O)CCC(F)(F)F PSRZMXNNQTWAGB-UHFFFAOYSA-N 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- 235000004416 zinc carbonate Nutrition 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
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/04—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid halides
-
- 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
- Y02P20/584—Recycling of catalysts
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A method for preparing 4, 4-trifluoro-butyric acid, which belongs to the technical field of fluorine-containing fine chemicals. The preparation method is characterized by comprising the following preparation steps: uniformly mixing 3,3 trifluoro propionyl chloride and a catalyst; the system is insulated to 10 ℃ to 25 ℃, and trimethylsilyl diazomethane solution is added dropwise, wherein the molar ratio of 3,3 trifluoro propionyl chloride to trimethylsilyl diazomethane is as follows: 1:1.0-1.5; after the dripping is completed, keeping the reaction temperature for continuous reaction for 2-6 h; then water is added dropwise, and the mole ratio of the water to the 3,3 trifluoro propionyl chloride is as follows: 0.95 to 1.1:1; and after the dripping is finished, continuing to react for 2 to 8 hours to obtain a crude product, and rectifying the crude product to obtain the 4, 4-trifluoro-butyric acid. The invention discloses a method for preparing TFBA by a one-pot method, which has mild reaction conditions and high safety, and solves the problems of high raw material price, difficult preparation and low production efficiency of the traditional TFBA preparation method.
Description
Technical Field
The invention belongs to the technical field of fluorine-containing fine chemicals, and relates to a method for preparing 4, 4-trifluoro-butyric acid.
Background
4, 4-trifluoro-butyric acid (TFBA) is an important pharmaceutical synthetic material and organofluoro material intermediate. The method is mainly used for synthesizing functional polymer materials and fluorine-containing fine chemicals. Such as fluorine-containing surfactant, fluorine grease, etc., has wide application prospect.
The pure TFBA is colorless and transparent acidic liquid with pungent smell, is extremely easy to absorb water and decompose in air, and has strong corrosiveness. TFBA formula C 4 H 5 F 3 O 2 Relative molecular weight 142.1, boiling point 166-167 ℃, melting point 30 ℃, liquid relative density 1.4g/mL.
The synthesis method of 4, 4-trifluoro butyric acid in the prior art mainly comprises the following synthesis routes:
the first is to prepare trifluorobutyric acid (Tetrahedron Letters,1989, vol.30, #33 p.4403-4406) using 1-iodo-3, 3-trifluoropropane and carbon monoxide as starting materials;
the second is to prepare trifluoro-butyric acid (Journal of Organic Chemistry,1983, vol.48, # 21p.3803-3807) using 3, 3-trifluoropropene and carbon monoxide as raw materials;
thirdly, 3-bromo-1, 1-trifluoropropane and carbon dioxide are used as raw materials to prepare trifluoro-butyric acid (Journal of the American Chemical Society,1988, vol.110, # 12p.4019-4022);
fourthly, preparing trifluoro butyric acid (Justus Liebigs Annalen der Chemie,1933, vol.506, p.33, 54) by using carbon tetrachloride and butyric acid as raw materials;
fifth, ethyl trifluorobutyrate was used to prepare trifluoro butyric acid by hydrolysis (US 5653990 a1,1997);
a sixth process for preparing trifluorobutyric acid (Journal of Organic Chemistry,1956, vol.21, p.1342, 1346) using trifluoropropyl magnesium chloride and ammonium bicarbonate;
seventh, ethyl trifluorobutenoate is used as a raw material to prepare trifluoro butyric acid (US 4552883 a1,1985);
eighth, trifluoro-butyric acid is prepared by decarboxylation of (2, 2-trifluoroethyl) malic acid (Tetrahedron, 1988, vol.44, # 17p.5375-5387).
The various methods described above have the following disadvantages: the acid wastewater generated by the reaction is more, and the method is not friendly to the environment; the catalyst is large in dosage and high in cost; the reaction conditions are harsh; the reaction process is longer; the product yield is low; the raw materials are difficult to prepare, and the price is high.
Disclosure of Invention
The invention aims to solve the technical problems that: overcomes the defects of the prior art, and provides a method for preparing 4, 4-trifluoro-butyric acid with mild reaction conditions, high safety and low cost.
The technical scheme adopted for solving the technical problems is as follows: a process for preparing 4, 4-trifluoro-butyric acid, characterized by the following steps:
1) Uniformly mixing 3,3 trifluoro propionyl chloride and a catalyst;
2) The system is insulated to 10 ℃ to 25 ℃, and trimethylsilyl diazomethane solution is added dropwise, wherein the molar ratio of 3,3 trifluoro propionyl chloride to trimethylsilyl diazomethane is as follows: 1:1.0-1.5; after the dripping is completed, keeping the reaction temperature for continuous reaction for 2-6 h;
3) Then water is added dropwise, and the mole ratio of the water to the 3,3 trifluoro propionyl chloride is as follows: 0.95 to 1.1:1; and after the dripping is finished, continuing to react for 2 to 8 hours to obtain a crude product, and rectifying the crude product to obtain the 4, 4-trifluoro-butyric acid.
The invention relates to a method for preparing TFBA by using 3, 3-trifluoro propionyl chloride, trimethylsilyl diazomethane and water as raw materials under the condition of a certain temperature and the existence of a catalyst. The reaction equation of the above reaction of the present invention:
the method has mild reaction conditions and high safety, and solves the problems of high raw material price, difficult preparation and low production efficiency of the traditional TFBA preparation method.
Preferably, in the above method for preparing 4, 4-trifluoro butyric acid, the catalyst in step 1) is silver oxide and zinc oxide in a molar ratio of 10: 3-8 composite aluminum-based catalyst, the addition amount of the catalyst is 0.5-1.5% of the mass of 3, 3-trifluoropropionyl chloride. The catalyst combines silver oxide and zinc oxide, combines the catalytic performance of the silver oxide and the zinc oxide through aluminum base combination, and can greatly improve the selectivity of the reaction and improve the preparation efficiency and the conversion rate. The preparation method of the aluminum-based catalyst comprises the following steps: silver oxide and zinc oxide are added into the high-purity sodium metaaluminate solution, and the molar ratio of the sodium metaaluminate to the silver oxide is 2-4: 1, adding the zinc oxide according to the proportion of silver oxide to zinc oxide set in the catalyst; introducing excessive carbon dioxide during stirring to form mixed precipitate of aluminum hydroxide, silver carbonate and zinc carbonate, directly crushing solid separated from solid and liquid, rounding into pills, and drying and calcining.
Optionally, in the method for preparing 4, 4-trifluoro-butyric acid, the catalyst in the step 1) is silver oxide, and the catalyst addition amount is 1% -3% of the mass of 3, 3-trifluoro-propionyl chloride. The silver oxide catalyst can meet the basic reaction catalysis of the invention, can ensure the reaction to be carried out under the addition amount, and has higher reaction rate and conversion rate.
Preferably, in the above method for preparing 4, 4-trifluoro-butyric acid, the trimethylsilyl diazomethane solution in step 2) is an n-hexane solution of trimethylsilyl diazomethane. After the trimethylsilyl diazomethane is dissolved into a solution by utilizing n-hexane, the materials are contacted uniformly, the system reaction is balanced, the overall preparation efficiency is higher, and the reaction is milder.
Preferably, in the above-mentioned method for producing 4, 4-trifluorobutyric acid, the reaction temperature in the step 2) is 20℃to 25 ℃. Under the preferred catalyst and solution conditions, slightly higher temperatures can be used to further accelerate the reaction rate without affecting the conversion.
Preferably, in the above method for preparing 4, 4-trifluoro-butyric acid, the total reaction time in step 2) and step 3) is 6 to 12 hours. The total reaction time is controlled, so that the overall conversion rate can be kept, the overlong reaction time can be prevented, and the preparation efficiency is ensured.
Preferably, in the above method for preparing 4, 4-trifluoro-butyric acid, the reaction pressure in step 2) and step 3) is normal pressure. The reaction of the invention can keep high efficiency and high conversion rate under normal pressure, the reaction condition is mild, and high pressure is not needed.
Preferably, in the above method for preparing 4, 4-trifluoro butyric acid, the system temperature is 10 ℃ to 15 ℃ and the dropping time is 1h to 2h when the trimethylsilyl diazomethane solution is dropped in the step 2). The dripping speed and the temperature of the trimethylsilyl diazomethane are controlled, so that the smooth start of the reaction can be ensured, the lower reaction speed is kept in the dripping process, the conversion rate is kept, and the side reaction is reduced.
Preferably, in the above method for preparing 4, 4-trifluoro-butyric acid, the rectification in step 3) is negative pressure rectification.
Preferably, in the above method for preparing 4, 4-trifluoro-butyric acid, the vacuum degree of the negative pressure rectification is-0.093 MPa to-0.095 MPa. By adopting negative pressure rectification with proper pressure, the separation efficiency can be improved.
Preferably, in the above method for preparing 4, 4-trifluorobutyric acid, the water and 3,3 trifluoropropionyl chloride in step 3) are in equimolar amounts.
Compared with the prior art, the method for preparing the 4, 4-trifluoro-butyric acid has the following beneficial effects: the preparation method of 4, 4-trifluoro butyric acid provided by the invention uses the raw material 3, 3-trifluoro propionyl chloride which is cheap and easy to obtain, and has already realized industrial production. The invention has simple reaction operation, high safety coefficient, mild synthesis process condition and higher yield.
Detailed Description
The present invention will be further described with reference to specific examples, wherein example 1 is the best practice, and the aluminum-based catalysts used in examples 1 to 3 are prepared by themselves in laboratories of new materials, inc. of Shandong Huaan, by the above-described processes, respectively.
Example 1
To a 1000mL four-necked flask equipped with a bulb condenser, thermometer and mechanical stirring were added 146.5g of 3, 3-trifluoropropionyl chloride and 1.5g of a catalyst comprising silver oxide and zinc oxide in a molar ratio of 10:4 a composite aluminum-based catalyst; dropwise adding 0.5L of trimethyl silicon-based diazomethane n-hexane solution with concentration of 2mol/L at the temperature of 10 ℃ in a bottle for 1h, and continuously stirring at 20 ℃ for 2h after the dropwise adding; 18.0g of water is added dropwise for 1h, and the reaction temperature is kept for continuous stirring and reaction for 2h after the completion of the dripping. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.093MPa to obtain 4, 4-trifluoro butyric acid with the purity of 98.6 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 93.4 percent.
Example 2
To a 1000mL four-necked flask equipped with a bulb condenser, thermometer and mechanical stirring were added 146.5g of 3, 3-trifluoropropionyl chloride and 0.75g of a catalyst comprising silver oxide and zinc oxide in a molar ratio of 10:3 a composite aluminum-based catalyst; dropwise adding 0.5L of trimethyl silicon-based diazomethane n-hexane solution with concentration of 2mol/L at the temperature of 10 ℃ in a bottle for 2 hours, and continuously stirring at 20 ℃ for reaction for 4 hours after the dropwise adding; 18.0g of water is added dropwise for 1h, and the reaction temperature is kept for continuous stirring and reaction for 2h after the completion of the dripping. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.095MPa to obtain 4, 4-trifluoro butyric acid with the purity of 98.5 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 93.7 percent.
Example 3
To a 1000mL four-necked flask equipped with a bulb condenser, thermometer and mechanical stirring were added 146.5g of 3, 3-trifluoropropionyl chloride and 2.25g of a catalyst comprising silver oxide and zinc oxide in a molar ratio of 10:8 a composite aluminum-based catalyst; dropwise adding 0.5L of trimethyl silicon-based diazomethane n-hexane solution with concentration of 2mol/L at the temperature of 12 ℃ in a bottle for 2 hours, and continuously stirring at 22 ℃ for reaction for 6 hours after the dropwise adding; 18.0g of water is added dropwise for 1h, and the reaction temperature is kept for continuous stirring and reaction for 2h after the completion of the dripping. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.093MPa to obtain 4, 4-trifluoro butyric acid with the purity of 98.7 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 93.3 percent.
Example 4
146.5g of 3, 3-trifluoropropionyl chloride and 1.5g of silver oxide are added into a 1000mL four-necked flask equipped with a spherical condenser tube, a thermometer and a mechanical stirrer, 0.5L of trimethyl silicon-based diazomethane n-hexane solution with the concentration of 2mol/L is dropwise added at the temperature of 13 ℃ in the flask, the dropwise addition time is 2 hours, after the dropwise addition, the stirring reaction is continued for 6 hours at the temperature of 23 ℃; 18.0g of water is added dropwise for 2 hours, and the reaction temperature is kept for continuous stirring and reaction for 2 hours after the dripping is finished. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.095MPa to obtain 4, 4-trifluoro butyric acid with the purity of 96.7 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 94.5%.
Example 5
146.5g of 3, 3-trifluoropropionyl chloride and 3.0g of silver oxide are added into a 1000mL four-necked flask equipped with a spherical condenser tube, a thermometer and a mechanical stirrer, 0.5L of trimethyl silicon-based diazomethane n-hexane solution with the concentration of 2mol/L is dropwise added at the temperature of 12 ℃ in the flask, the dropwise addition time is 2 hours, after the dropwise addition, the stirring reaction is continued for 6 hours at the temperature of 22 ℃; 18.0g of water is added dropwise for 2 hours, and the reaction temperature is kept for continuous stirring and reaction for 2 hours after the dripping is finished. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.095MPa to obtain 4, 4-trifluoro butyric acid with the purity of 96.8 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 96.1 percent.
Example 6
146.5g of 3, 3-trifluoropropionyl chloride and 4.5g of silver oxide are added into a 1000mL four-necked flask equipped with a spherical condenser tube, a thermometer and a mechanical stirrer, 0.5L of trimethyl silicon-based diazomethane n-hexane solution with the concentration of 2mol/L is dropwise added at the temperature of 15 ℃ in the flask, the dropwise addition time is 2 hours, after the dropwise addition, the stirring reaction is continued for 6 hours at the temperature of 25 ℃; 18.0g of water is added dropwise for 2 hours, and the reaction temperature is kept for continuous stirring and reaction for 2 hours after the dripping is finished. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.095MPa to obtain 4, 4-trifluoro butyric acid with the purity of 97.0 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 95.4 percent.
Example 7
146.5g of 3, 3-trifluoropropionyl chloride and 3.0g of silver oxide are added into a 1000mL four-necked flask equipped with a spherical condenser tube, a thermometer and a mechanical stirrer, 0.55L of trimethyl silicon-based diazomethane n-hexane solution with the concentration of 2mol/L is dropwise added at the temperature of 10 ℃ in the flask, the dropwise addition time is 2 hours, after the dropwise addition, the continuous stirring reaction is carried out for 6 hours at the temperature of 20 ℃; 18.0g of water is added dropwise for 2 hours, and the reaction temperature is kept for continuous stirring and reaction for 2 hours after the dripping is finished. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.093MPa to obtain 4, 4-trifluoro butyric acid with the purity of 96.7 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 96.0%.
Example 8
146.5g of 3, 3-trifluoropropionyl chloride and 3.0g of silver oxide are added into a 1000mL four-necked flask equipped with a spherical condenser tube, a thermometer and a mechanical stirrer, 0.65L of trimethyl silicon-based diazomethane n-hexane solution with the concentration of 2mol/L is dropwise added at the temperature of 15 ℃ in the flask, the dropwise addition time is 2 hours, after the dropwise addition, the stirring reaction is continued for 6 hours at the temperature of 25 ℃; 18.0g of water is added dropwise for 2 hours, and the reaction temperature is kept for continuous stirring and reaction for 2 hours after the dripping is finished. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.095MPa to obtain 4, 4-trifluoro butyric acid with the purity of 96.2 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 94.2 percent.
Example 9
146.5g of 3, 3-trifluoropropionyl chloride and 3.0g of silver oxide are added into a 1000mL four-necked flask equipped with a spherical condenser tube, a thermometer and a mechanical stirrer, 0.75L of trimethyl silicon-based diazomethane n-hexane solution with the concentration of 2mol/L is dropwise added at the temperature of 10 ℃ in the flask, the dropwise addition time is 2 hours, after the dropwise addition, the stirring reaction is continued for 6 hours at the temperature of 20 ℃; 18.0g of water is added dropwise for 2 hours, and the reaction temperature is kept for continuous stirring and reaction for 2 hours after the dripping is finished. After the reaction is finished, carrying out negative pressure rectification on the system under the condition of minus 0.093MPa to obtain 4, 4-trifluoro butyric acid with the purity of 95.7 percent. 3, 3-trifluoro propionyl chloride is taken as a substrate, and the yield is 92.1 percent.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the invention in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to the equivalent embodiments. However, any simple modification, equivalent variation and variation of the above embodiments according to the technical substance of the present invention still fall within the protection scope of the technical solution of the present invention.
Claims (10)
1. A method for preparing 4, 4-trifluoro-butyric acid, which is characterized by comprising the following preparation steps:
1) Uniformly mixing 3,3 trifluoro propionyl chloride and a catalyst;
2) The system is insulated to 10 ℃ to 25 ℃, and trimethylsilyl diazomethane solution is added dropwise, wherein the molar ratio of 3,3 trifluoro propionyl chloride to trimethylsilyl diazomethane is as follows: 1:1.0-1.5; after the dripping is completed, keeping the reaction temperature for continuous reaction for 2-6 h;
3) Then water is added dropwise, and the mole ratio of the water to the 3,3 trifluoro propionyl chloride is as follows: 0.95 to 1.1:1; and after the dripping is finished, continuing to react for 2 to 8 hours to obtain a crude product, and rectifying the crude product to obtain the 4, 4-trifluoro-butyric acid.
2. A process for preparing 4, 4-trifluoro-butyric acid according to claim 1, wherein: the catalyst in the step 1) is silver oxide and zinc oxide according to the mol ratio of 10: 3-8 composite aluminum-based catalyst, the addition amount of the catalyst is 0.5-1.5% of the mass of 3, 3-trifluoropropionyl chloride.
3. A process for preparing 4, 4-trifluoro-butyric acid according to claim 1, wherein: the trimethylsilyl diazomethane solution in the step 2) is an n-hexane solution of trimethylsilyl diazomethane.
4. A process for preparing 4, 4-trifluoro-butyric acid according to claim 1, wherein: the reaction temperature in the step 2) is 20-25 ℃.
5. A process for preparing 4, 4-trifluoro-butyric acid according to claim 1, wherein: the total reaction time in the step 2) and the step 3) is 6-12 h.
6. A process for preparing 4, 4-trifluoro-butyric acid according to claim 1, wherein: the pressure of the reaction in the step 2) and the step 3) is normal pressure.
7. A process for preparing 4, 4-trifluoro-butyric acid according to claim 1, wherein: and 2) dropwise adding the trimethylsilyl diazomethane solution in the step 2), wherein the system temperature is 10-15 ℃ and the dropwise adding time is 1-2 h.
8. A process for preparing 4, 4-trifluoro-butyric acid according to claim 1, wherein: the rectification in the step 3) is negative pressure rectification.
9. A process for preparing 4, 4-trifluoro-butyric acid according to claim 8, wherein: the vacuum degree of the negative pressure rectification is-0.093 MPa to-0.095 MPa.
10. A process for preparing 4, 4-trifluoro-butyric acid according to claim 1, wherein: the water and 3,3 trifluoropropionyl chloride in step 3) are in equimolar amounts.
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| CN116768696A (en) * | 2023-08-25 | 2023-09-19 | 山东华安新材料有限公司 | Method for preparing high-purity 1,3, 5-trifluoro benzene by one-step method |
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