CN110845342B - Preparation method of anhydrous tetrabutylammonium fluoride - Google Patents
Preparation method of anhydrous tetrabutylammonium fluoride Download PDFInfo
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- CN110845342B CN110845342B CN201910758403.5A CN201910758403A CN110845342B CN 110845342 B CN110845342 B CN 110845342B CN 201910758403 A CN201910758403 A CN 201910758403A CN 110845342 B CN110845342 B CN 110845342B
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Abstract
The invention discloses a preparation method of anhydrous tetrabutylammonium fluoride, which is characterized by comprising the following steps: dissolving water-containing tetrabutylammonium fluoride in an organic solvent, carrying out azeotropic water-carrying through a water separator for 30-180 minutes, then evaporating the solvent, adding the same solvent with the same volume, carrying out reduced pressure distillation, adding THF (tetrahydrofuran) into the solid obtained after twice operation, removing the solvent under reduced pressure after dissolution, and finally cooling at-10 ℃ to separate out a solid, namely the anhydrous TBAF; the invention directly uses the existing tetrabutylammonium fluoride trihydrate for refining, removes water by an azeotropic water-carrying mode through an organic solvent, and then obtains the target product anhydrous tetrabutylammonium fluoride by a low-temperature cooling crystallization mode, thereby solving the complex process in the original preparation process of the anhydrous tetrabutylammonium fluoride and having low production cost.
Description
The technical field is as follows:
the invention discloses a preparation method of anhydrous tetrabutylammonium fluoride, belonging to the technical field of chemical synthesis.
Background art:
tetrabutylammonium fluoride ((CH)3CH2CH2CH2)4N+F-TBAF), a quaternary ammonium salt that is very hygroscopic, usually in the form of trihydrate. Since fluoride ion is a very strong hydrogen bond acceptor, water cannot be removed by simple distillation under reduced pressure, and beta-dehydrogenation elimination reaction to Hydrogen Fluoride (HF) occurs when heated to 77 ℃ under high vacuum2 -) Whereas the product obtained under vacuum drying at low temperature (40 ℃) contains 10-30 mol% of bound water and about 10% of hydrogen fluoride, so that it is significant to prepare anhydrous TBAF. The existing method for preparing anhydrous TBAF only has one reaction reported in 2005,according to the method, tetrabutylammonium cyanide and hexafluorobenzene are subjected to nucleophilic substitution reaction at a low temperature, hexafluorobenzene is dropwise added at a temperature of-65 ℃ and then reacts at a temperature of-15 ℃ for four hours to prepare a white solid, the white solid is filtered at the temperature of-65 ℃ and is washed by Tetrahydrofuran (THF), and the obtained anhydrous TBAF can be stored at the temperature of-36 ℃ (J.AM.CHEM.SOC.2005,127, 2050-2051). The cost of the TBAF prepared by the method is too high, and the TBAF cannot be produced in a large scale, so that the method for finding the anhydrous TBAF which is simple and convenient and can be industrially produced is particularly important.
The invention content is as follows:
the invention aims to provide a preparation method of anhydrous tetrabutylammonium fluoride, which has high efficiency, low water content and low cost and can be industrialized.
The technical scheme adopted by the invention is as follows:
a preparation method of anhydrous tetrabutylammonium fluoride is characterized by comprising the following steps: dissolving water-containing tetrabutylammonium fluoride in an organic solvent, carrying out azeotropic distillation on the solution for 30-60 minutes by using a water separator, then evaporating the solvent, adding the same solvent with the same volume, carrying out reduced pressure distillation, adding THF (tetrahydrofuran) into the solid obtained after twice operation, removing the solvent under reduced pressure after dissolution, and finally cooling at-10 ℃ to separate out a solid, namely the anhydrous TBAF.
Further settings are as follows:
the aqueous tetrabutylammonium fluoride is tetrabutylammonium fluoride trihydrate or higher.
The organic solvent is one of tetrahydrofuran, methyltetrahydrofuran, acetonitrile, dichloromethane and 1, 2-dichloroethane, wherein the preferred solvent is 1, 2-dichloroethane or tetrahydrofuran.
The azeotropic entrainment of water was carried out under argon protection.
The azeotropic entrainment of water is carried out at a pressure of from 0.01 to 0.07 MPa.
The resulting solid was drained and then stored as a THF solution. (since anhydrous TBAF cannot be preserved for a long time, the product was prepared into a solution for storage after it was obtained)
A preparation method of anhydrous tetrabutylammonium fluoride is characterized by comprising the following steps: dissolving 20g of tetrabutylammonium fluoride trihydrate sample in 40mL of 1, 2-dichloroethane, reducing the pressure at 55 ℃ under the protection of argon through a water separator until the vacuum degree is 0.02MPa, carrying out water carrying for 1 hour, then removing the solvent under reduced pressure, measuring the water content to be 7.2%, adding 30mL of 1, 2-dichloroethane, distilling at 55 ℃ under reduced pressure to remove the solvent, repeating the steps for 5 times, cooling to-10 ℃ under argon to obtain TBAF solid, carrying out suction filtration, washing twice with a precooled THF solution, and obtaining 15.1g of the target anhydrous TBAF solid, wherein the yield is 90%, the purity is 99.1%, and the water content is 0.8%.
A preparation method of anhydrous tetrabutylammonium fluoride is characterized by comprising the following steps: dissolving 20g of tetrabutylammonium fluoride trihydrate sample in 20mL of tetrahydrofuran, carrying out pressure reduction and water carrying for 1 hour at 65 ℃ through a water separator under the protection of argon, controlling the vacuum degree when carrying out pressure reduction and water carrying, leading the reflux speed of the solvent to be 1-2 drops per second, then removing the solvent, measuring the water content to be 9.2%, then adding 20mL of THF, carrying out pressure reduction and water carrying, distilling to remove the solvent, repeating for 3-5 times, cooling to-10 ℃ under argon to obtain TBAF solid, carrying out suction filtration, washing twice with a precooled THF solution, and obtaining 13.2g of the target anhydrous TBAF solid, wherein the yield is 77%, the purity is 97.2%, and the water content is 2.3%.
The invention has the following beneficial effects:
the invention directly uses the existing tetrabutylammonium fluoride trihydrate for refining, removes water by an azeotropic water-carrying mode through an organic solvent, and then obtains the target product anhydrous tetrabutylammonium fluoride (tetrabutylammonium fluoride solid with the water content lower than 1%) by a low-temperature cooling crystallization mode.
The present invention will be further described with reference to the following detailed description.
The specific implementation mode is as follows:
example 1:
20g of tetrabutylammonium fluoride trihydrate sample is dissolved in 20mL of tetrahydrofuran, water is brought under the protection of argon at 65 ℃ through a water separator under reduced pressure (the vacuum degree is controlled, the solvent reflux speed is controlled to be 1-2 drops per second) for 1 hour, then the solvent is removed, the water content is measured to be 9.2%, then 20mL of THF is added, water is brought under reduced pressure, the solvent is distilled off, the reaction is repeated for 3-5 times, the reaction product is cooled to-10 ℃ under argon to obtain TBAF solid, the TBAF solid is subjected to suction filtration and washed twice by a small amount of pre-cooled THF solution, and 13.2g of the target anhydrous TBAF solid is obtained, the yield is 77%, the purity is 97.2%, and the water content is 2.3%.
Based on example 1, the kind of azeotropic solvent was adjusted, and the influence thereof on the water content and purity of the product was tested, and the results are shown in table 1.
Table 1:
| serial number | Type of solvent | Yield/g | Water content/%) | Purity/%) |
| Alternative example 1-1 | 1, 2-dichloroethane | 14.9 | 2.7 | 98.1 |
| Alternative examples 1 to 2 | Methyl tetrahydrofuran | 15.8 | 1.8 | 97.6 |
| Alternative examples 1 to 3 | Toluene | 16.3 | 16.3 | 83.5 |
| Alternative examples 1 to 3 | Benzene and its derivatives | 16.5 | 16.6 | 82.7 |
。
As shown in table 1:
different organic solvents have great difference in water removal effect, such as alcohol compounds, which can not be used as solvents for azeotropic water removal due to reaction with tetrabutylammonium fluoride; although toluene does not react, the azeotropic water removal effect is not obvious through experiments, and the same is true when benzene is used. Repeated experiments of the applicant find that the water removal solvent only comprises tetrahydrofuran, methyltetrahydrofuran and 1, 2-dichloroethane, and the effect is optimal.
Example 2:
20g of tetrabutylammonium fluoride trihydrate sample is dissolved in 40mL of 1, 2-dichloroethane, the mixture is subjected to reduced pressure (the vacuum degree is 0.02MPa) at 55 ℃ under the protection of argon and water for 1 hour through a water separator, then the solvent is removed under reduced pressure, the water content is measured to be 7.2%, 30mL of 1, 2-dichloroethane is added, the solvent is removed by reduced pressure distillation at the same temperature, after 5 times of repetition, the mixture is cooled to-10 ℃ under argon to obtain TBAF solid, and the TBAF solid is subjected to suction filtration and washed twice by a small amount of pre-cooled THF solution to obtain 15.1g of the target anhydrous TBAF solid, the yield is 90%, the purity is 99.1%, and the water content is 0.8%.
Based on example 2, the amount of 1, 2-dichloroethane was adjusted and the amount and number of times of the solvent carrying water and the temperature and time of azeotropic carrying water were repeated thereafter, and the influence thereof on the water content and purity of the product was examined, and the results are shown in Table 1.
Table 2:
as shown in table 2:
the selection of solvent, the temperature of water removal and the time of water separation all have influence on the yield:
generally speaking, higher temperature can obtain better water removal effect, and experiments show that the water removal effect is good when the temperature is higher than 55 ℃, but the product can be decomposed along with the further increase of the temperature, so that the yield is influenced, and at the moment, the higher the temperature is, the lower the yield is,
as shown in table 2, when a water diversion experiment is performed at 55 ℃, under the condition that the solvent amount is determined, the water diversion time is increased, the yield is not greatly influenced, but the water content can be effectively reduced, and in addition, the increase of the solvent amount is also beneficial to reducing the water content of the TBAF.
Comprehensively considering: the experimental conditions of example 2 are the best examples, namely: the dosage of the solvent is 40mL, the temperature of water removal is 55 ℃, the time of water removal is 1 hour, then the solvent is used for dissolving, the reduced pressure distillation is carried out for 5 times, and the cooling crystallization is carried out.
Example 3:
200g of tetrabutylammonium fluoride sample is dissolved in 400mL of 1, 2-dichloroethane, the mixture is directly heated to 55 ℃ under the vacuum degree of 0.02MPa, reduced pressure distillation is carried out for 1 hour, the solvent is removed under reduced pressure, the water content is measured to be 7.6%, then 300mL of the dissolved product of the 1, 2-dichloroethane is continuously added, reduced pressure distillation at 55 ℃ is carried out for slowly removing the water, and after repeating for 4 times, 150.3g of tetrabutylammonium fluoride with the water content of 1.0% is obtained, and the purity is 98.8%.
Comparative example 1:
20g of tetrabutylammonium fluoride crystal recrystallized by water is heated to 80 ℃ under 0.01MPa and is distilled under reduced pressure for 2 hours, and a sample solution is taken to detect the moisture, so that the water content is 15.1 percent and the tetrabutylammonium fluoride content is 81.6 percent. 3.3 percent of decomposition product.
The temperature and time were adjusted and the dewatering effect was measured as shown in table 3:
table 3:
| serial number | Temperature/. degree.C | Time per hour | Moisture/% (moisture converted to solid) | Decomposition rate/%) |
| Comparative examples 1 to 1 | 80 | 4 | 14.2 | 7.3 |
| Comparative examples 1 to 2 | 95 | 2 | 9.8 | 10.1 |
| Comparative examples 1 to 3 | 100 | 3 | 9.1 | 15.2 |
| Comparative examples 1 to 4 | 65 | 5 | 16.1 | 1.1 |
。
As shown in table 3:
the method of direct reduced pressure distillation water removal is adopted, and at a lower temperature, although the product is relatively stable, the water removal effect is not obvious; the water removal effect is improved to a certain extent with the increase of the temperature, but the further increase of the temperature causes a great deal of decomposition of the product, and the water content cannot be reduced continuously after about 9 percent.
Comparative example 2:
a20 g sample of tetrabutylammonium fluoride trihydrate was dissolved in 20mL of tetrahydrofuran, dried over anhydrous magnesium sulfate, molecular sieves, and a super absorbent resin, and the results of water removal were shown in Table 4 below:
table 4:
| serial number | Drying agent | Dosage per gram | Moisture/% (moisture converted to solid) |
| Comparative example 2-1 | Anhydrous magnesium sulfate | 10 | 16.8 |
| Comparative examples 2 to 2 | Molecular sieves | 10 | 16.7 |
| Comparative examples 2 to 3 | Molecular sieves | 20 | 16.5 |
| Comparative examples 2 to 4 | High water absorption resin | 10 | 16.3 |
| Comparative examples 2 to 5 | High water absorption resin | 20 | 15.9 |
。
As shown in table 4:
the drying and dewatering mode of the drying agent is adopted, the dewatering effect is limited, only a small amount of moisture can be removed, and even if the using amount of the drying agent is increased, the improvement of the dewatering effect is not obvious, so that the drying agent has no industrial application value.
Claims (6)
1. A preparation method of anhydrous tetrabutylammonium fluoride is characterized by comprising the following steps: dissolving water-containing tetrabutylammonium fluoride in an organic solvent, carrying out azeotropic water-carrying through a water separator for 30-180 minutes, then evaporating the solvent, adding the same solvent with the same volume, carrying out reduced pressure distillation, adding THF (tetrahydrofuran) into the solid obtained after twice operation, removing the solvent under reduced pressure after dissolution, and finally cooling at-10 ℃ to separate out a solid, namely the anhydrous TBAF;
the organic solvent is one of tetrahydrofuran, methyltetrahydrofuran and 1, 2-dichloroethane;
the water separator carries water, the water removal temperature is 55 ℃, and the water separation time is 1 hour.
2. The method according to claim 1, wherein the method comprises the following steps: the aqueous tetrabutylammonium fluoride is tetrabutylammonium fluoride trihydrate or higher.
3. The method according to claim 1, wherein the method comprises the following steps: the azeotropic entrainment of water was carried out under argon protection.
4. The method according to claim 1, wherein the method comprises the following steps: the azeotropic entrainment of water is carried out at a pressure of 0.01 to 0.07 MPa.
5. The method according to claim 1, wherein the method comprises the following steps: the resulting solid was drained and stored as a THF solution.
6. The method according to claim 1, wherein the method comprises the following steps: dissolving 20g of tetrabutylammonium fluoride trihydrate sample in 40mL of 1, 2-dichloroethane, reducing the pressure at 55 ℃ under the protection of argon through a water separator until the vacuum degree is 0.02MPa, carrying out water carrying for 1 hour, then removing the solvent under reduced pressure, measuring the water content to be 7.2%, adding 30mL of 1, 2-dichloroethane, distilling at 55 ℃ under reduced pressure to remove the solvent, repeating the steps for 5 times, cooling to-10 ℃ under argon to obtain TBAF solid, carrying out suction filtration, washing twice with a precooled THF solution, and obtaining 15.1g of the target anhydrous TBAF solid, wherein the yield is 90%, the purity is 99.1%, and the water content is 0.8%.
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| CN104803858A (en) * | 2014-01-23 | 2015-07-29 | 东莞市长安东阳光铝业研发有限公司 | Method used for preparing tetrabutylammonium fluoride trihydrate |
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| CN104803858A (en) * | 2014-01-23 | 2015-07-29 | 东莞市长安东阳光铝业研发有限公司 | Method used for preparing tetrabutylammonium fluoride trihydrate |
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| Title |
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| Tetrabutylammonium fluoride;Li, Hui-Yin等;《e-EROS Encyclopedia of Reagents for Organic Synthesis》;20071231;第1页左栏 * |
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