CN113943208A - Preparation method of 3,3, 3-trifluoropropanol - Google Patents
Preparation method of 3,3, 3-trifluoropropanol Download PDFInfo
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- CN113943208A CN113943208A CN202111479743.8A CN202111479743A CN113943208A CN 113943208 A CN113943208 A CN 113943208A CN 202111479743 A CN202111479743 A CN 202111479743A CN 113943208 A CN113943208 A CN 113943208A
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- trifluoropropanol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/36—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring increasing the number of carbon atoms by reactions with formation of hydroxy groups, which may occur via intermediates being derivatives of hydroxy, e.g. O-metal
Abstract
The invention relates to a preparation method of 3,3, 3-trifluoropropanol, belonging to the technical field of organic fluorine chemical industry. According to the preparation method of the 3,3, 3-trifluoropropanol, the 3,3, 3-trifluoropropanol is prepared by carrying out Grignard reaction on the epoxypropane and the methyl magnesium bromide, the raw materials are easily available and sold on the market, and the preparation process of Grignard reagents is mature. Has the advantages of simple process (one-pot method), high reaction conversion rate, easy realization of industrialization and the like. Solves the problem that the raw materials have defects in the production process of enterprises, and is beneficial to safe production. Short reaction flow, safety, environmental protection and less side reaction. Can continuously feed and is easy to realize large-scale industrial co-production.
Description
Technical Field
The invention relates to a preparation method of 3,3, 3-trifluoropropanol, belonging to the technical field of organic fluorine chemical industry.
Background
The molecular formula of the 3,3, 3-trifluoropropanol is C3H5F3O, molecular mass 114.07, CAS number 2240-88-2, density 1.30g/cm3Boiling point of 100 ℃ and flash point of 37.0 ℃, is an important trifluoromethyl building block reagent and is mainly used as medicine, pesticide and other reagentsThe raw material for synthesizing fluorine-containing material can also be used as solvent and additive. The structural formula is as follows:
the prior art 3,3, 3-trifluoropropanol includes mainly trifluoropropene process, chlorotrifluoropropene process, trifluorochloropropane process and trifluoroiodomethane process, the trifluoropropene process prepares 3,3, 3-trifluoropropanol by reducing 3,3, 3-trifluoropropionaldehyde, the 3,3, 3-trifluoropropionaldehyde is generally obtained by 3,3, 3-trifluoropropenylmethyl ether, 3,3, 3-trifluoropropene is taken as a starting raw material to prepare 3,3, 3-trifluoropropanol, and the synthetic route is as follows:
for example, in Chinese patent CN 105399607A, 3, 3-trifluoropropene is used as a starting material, and 3,3, 3-trifluoropropanol is prepared, and the total yield is only 63.3%. The trifluoropropene method needs liquid bromine to participate in the reaction process, and the trifluoropropene has the defects of flammability and explosiveness.
The difference of the monochlorotrifluoropropene method lies in that the synthesis raw materials of 3,3, 3-trifluoropropenylmethyl ether as an intermediate are different, Duyonmei and the like, the synthesis of trifluoropropenylmethyl ether, in the chemical world, the 8 th stage [ J ]. p483-485 in 2013 reports a method for preparing 3,3, 3-trifluoropropenylmethyl ether by monochlorotrifluoropropene, and other steps are basically the same. CN102766025 discloses a method for preparing 3,3, 3-trifluoropropanol from 3,3, 3-trifluoropropenyl methyl ether, and a synthetic route of the method is as follows:
US5777184 and US6111139 also disclose the preparation of 3,3, 3-trifluoropropanol using monochlorotrifluoropropene. The monochlorotrifluoropropene has the defects of easy self-polymerization and instability, thereby influencing the application of the monochlorotrifluoropropene method to a certain extent.
The preparation method of 3,3, 3-trifluoropropanol in the prior art also comprises a trifluorochloropropane method and a trifluoroiodomethane method, and the two preparation equations have the problem of high raw material price. Chinese patent CN102040480 discloses a method for synthesizing carboxylic ester of 3,3, 3-trifluoropropanol by reacting 3,3, 3-trifluoro-1-chloropropane with alkali metal salt of carboxylic acid, and hydrolyzing the carboxylic ester of 3,3, 3-trifluoropropanol to obtain 3,3, 3-trifluoropropanol. Organic Letters,4(26),4671-4672, 2002 discloses a method for synthesizing trifluoropropene from trifluoroiodomethane, ethylene sulfate and tetra-tri (dimethylamino) ethylene.
The trifluoropropene has the defects of flammability and explosiveness, the monochlorotrifluoropropene has the defects of easiness in self-polymerization and instability, and the chloropropane and the iodotrifluoromethane have the defects of high price of raw materials. Due to the adoption of multiple reactions, the synthesis method also has the defect of long synthesis steps, and the 3,3, 3-trifluoropropanol has low yield and the like. Therefore, the defects of instability, high price and low yield of the utilized raw materials in the existing preparation method can be overcome, and the preparation method of the 3,3, 3-trifluoropropanol which can be industrially applied and popularized is in urgent need to be developed.
Disclosure of Invention
In order to overcome the technical defects of the prior art that a raw material for preparing the 3,3, 3-trifluoropropanol is flammable and explosive, has instability, high cost, low yield, is not suitable for industrial production and the like, the invention provides the preparation method of the 3,3, 3-trifluoropropanol, and the preparation method has the advantages of simple process, few side reactions in the reaction process, high reaction yield, easiness in realizing industrialization and the like.
In order to achieve the purpose, the technical scheme adopted by the invention for solving the technical problem is that the preparation method of the 3,3, 3-trifluoropropanol comprises the following steps: in a reactor filled with inert gas, taking ethylene oxide and trifluoromethyl magnesium chloride as reactants, carrying out a formatting reaction to obtain a crude product of 3,3, 3-trifluoropropanol, and purifying to obtain a finished product of 3,3, 3-trifluoropropanol, wherein the reaction equation is as follows:
the reaction temperature of the formatting reaction is-20-0 ℃, and preferably-10-0 ℃.
The inert gas is one or more of helium, neon, argon, krypton, xenon, radon and nitrogen, and preferably nitrogen.
Preferably, the reaction vessel requires anhydrous, oxygen-free conditions.
The reaction solvent of the Grignard reaction is one or more of diethyl ether, propyl ether, butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methyl tert-butyl ether and the like, and tetrahydrofuran is preferred.
The formatted reaction solvent is anhydrous and anaerobic, and preferably the reaction solvent is dehydrated before use, with the water content controlled to be less than 50 ppm.
Preferably, the ethylene oxide is a tetrahydrofuran solution of ethylene oxide. The tetrahydrofuran solution of the raw material ethylene oxide adopts a pump feeding mode, and the feeding speed is strictly controlled.
Preferably, the mass ratio concentration of the tetrahydrofuran solution of the ethylene oxide is 10-15%.
The molar ratio of the ethylene oxide to the trifluoromethyl magnesium chloride is 0.9-2.0:1, preferably 1:1 +/-0.05.
The methyl magnesium chloride reagent can not be stored for a long time, and preferably is purchased in place before use. The raw material ethylene oxide is dried before use.
Preferably, the distillate is added to a dilute solution of ice hydrochloric acid after the formatting reaction is complete.
Preferably, the concentration of the ice dilute hydrochloric acid solution is 2% -35%, preferably 5% -10%.
Preferably, the temperature of the ice dilute hydrochloric acid solution is 0-5 ℃.
The invention has the beneficial technical effects that:
1. according to the preparation method of the 3,3, 3-trifluoropropanol, the 3,3, 3-trifluoropropanol is prepared by carrying out Grignard reaction on the epoxypropane and the methyl magnesium bromide, the raw materials are easily available and sold on the market, and the preparation process of Grignard reagents is mature.
2. The preparation method of the 3,3, 3-trifluoropropanol has the advantages of simple process (one-pot method), high reaction conversion rate, easy realization of industrialization and the like.
3. The invention provides a new method for synthesizing 3,3, 3-trifluoropropanol, which solves the problem that raw materials have defects in the production process of enterprises and is beneficial to safe production.
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the invention.
Selecting the best proportion of reactants
Example 1:
in a dry reaction vessel, under the protection of nitrogen, 900mL (1.8 mol) of a tetrahydrofuran solution of 2.0mol/L magnesium trifluoromethyl chloride was added as a reaction substrate, followed by stirring, cooling to-10 ℃ and adding a mixture of 66.10g (1.50 mol) of ethylene oxide and 420mL of tetrahydrofuran. After the addition, the temperature is slowly raised to 0 ℃ and the reaction lasts for 10 hours. Sampling to monitor ethylene oxide content below 0.1%, purification, sampling with ice diluted hydrochloric acid, GC analysis of 99.2% (area normalization) to give 160.33g of a colourless liquid, 3,3, 3-trifluoropropanol, 93.76% yield
Example 2:
3,3, 3-trifluoropropanol was synthesized with a yield of 95.20% according to the procedure and conditions of example 1, changing the ratio of methyl magnesium chloride to ethylene oxide of example 1 to 1: 1.
Example 3:
3,3, 3-Trifluoropropanol was synthesized with a yield of 95.09% according to the procedure and conditions of example 1, changing the ratio of tetramethylmagnesium chloride to trifluoroacetaldehyde of example 1 to 1.5: 1.
Selection of solvent type
Example 4:
3,3, 3-trifluoropropanol was synthesized with a yield of 92.03% by changing the tetrahydrofuran of example 1 into diethyl ether according to the procedure and conditions of example 1.
Example 5:
3,3, 3-Trifluoropropanol was synthesized with a yield of 95.05% by changing the tetrahydrofuran of example 1 to methyl t-butyl ether according to the procedure and conditions of example 1.
Selection of reaction temperature
Example 6:
3,3, 3-trifluoropropanol was synthesized with a yield of 76.03% according to the procedure and conditions of example 1, changing the reaction temperature of example 1 from 0 ℃ to 10 ℃.
Example 7:
3,3, 3-Trifluoropropanol was synthesized with a yield of 45.02% according to the procedure and conditions of example 1, changing the reaction temperature of example 1 from 0 ℃ to 20 ℃.
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 3,3, 3-trifluoropropanol is characterized by comprising the following steps: in a reactor filled with inert gas, taking ethylene oxide and trifluoromethyl magnesium chloride as reactants, carrying out a formatting reaction to obtain a crude product of 3,3, 3-trifluoropropanol, and purifying to obtain a finished product of 3,3, 3-trifluoropropanol, wherein the reaction equation is as follows:
2. a process for the preparation of 3,3, 3-trifluoropropanol according to claim 1, characterized in that: the reaction temperature of the formatting reaction is-20-0 ℃.
3. A process for the preparation of 3,3, 3-trifluoropropanol according to claim 1, characterized in that: the reaction solvent of the formatting reaction is one or more of diethyl ether, propyl ether, butyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, methyl tert-butyl ether and the like.
4. A process for the preparation of 3,3, 3-trifluoropropanol according to claim 3, characterized in that: the formatted reaction solvent needs to be dehydrated before use, with the water content controlled to be less than 50 ppm.
5. A process for the preparation of 3,3, 3-trifluoropropanol according to claim 1, characterized in that: the ethylene oxide is tetrahydrofuran solution of ethylene oxide.
6. A process for the preparation of 3,3, 3-trifluoropropanol according to claim 5, characterized in that: the tetrahydrofuran solution of the ethylene oxide is 10-15% in mass ratio concentration.
7. A process for the preparation of 3,3, 3-trifluoropropanol according to claim 1, characterized in that: the molar ratio of the ethylene oxide to the trifluoromethyl magnesium chloride is 0.9-2.0: 1.
8. A process for the preparation of 3,3, 3-trifluoropropanol according to claim 7, wherein: the molar ratio of the ethylene oxide to the trifluoromethyl magnesium chloride is 1:1 +/-0.05.
9. A process for the preparation of 3,3, 3-trifluoropropanol according to claim 1, characterized in that: after the formatting reaction was complete, the distillate was added to a dilute solution of ice in hydrochloric acid.
10. A process for the preparation of 3,3, 3-trifluoropropanol according to claim 9, characterized in that: the concentration of the ice dilute hydrochloric acid solution is 2-35%, and the solution temperature is 0-5 ℃.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073268A (en) * | 2022-06-30 | 2022-09-20 | 上海瑞合达医药科技有限公司 | 3,3, 3-trifluoropropanol and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698633A (en) * | 2009-11-13 | 2010-04-28 | 江苏工业学院 | Method for preparing trifluoromethyl benzyl alcohol by Grignard reaction |
| CN102040480A (en) * | 2010-11-16 | 2011-05-04 | 巨化集团公司 | Synthetic method of 3,3,3-trifluoropropanol |
| CN104860795A (en) * | 2015-04-21 | 2015-08-26 | 苏州久王环保科技股份有限公司 | Preparation method for 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl-1-ol |
| CN105399607A (en) * | 2015-11-06 | 2016-03-16 | 西安近代化学研究所 | Method for preparing 3,3,3-trifluoro propanol |
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- 2021-12-07 CN CN202111479743.8A patent/CN113943208A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101698633A (en) * | 2009-11-13 | 2010-04-28 | 江苏工业学院 | Method for preparing trifluoromethyl benzyl alcohol by Grignard reaction |
| CN102040480A (en) * | 2010-11-16 | 2011-05-04 | 巨化集团公司 | Synthetic method of 3,3,3-trifluoropropanol |
| CN104860795A (en) * | 2015-04-21 | 2015-08-26 | 苏州久王环保科技股份有限公司 | Preparation method for 3,4,4,4-tetrafluoro-3-(trifluoromethyl)butyl-1-ol |
| CN105399607A (en) * | 2015-11-06 | 2016-03-16 | 西安近代化学研究所 | Method for preparing 3,3,3-trifluoro propanol |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115073268A (en) * | 2022-06-30 | 2022-09-20 | 上海瑞合达医药科技有限公司 | 3,3, 3-trifluoropropanol and preparation method thereof |
| CN115073268B (en) * | 2022-06-30 | 2024-03-12 | 上海瑞合达医药科技有限公司 | 3, 3-trifluoropropanol and preparation method thereof |
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