阅读说明：本技术 一种无水四丁基氟化铵的制备方法 (Preparation method of anhydrous tetrabutylammonium fluoride ) 是由 王新伟 沈永淼 李青山 施旭升 董柱永 吴尖平 奚紫微 泮啸楚 于 2019-08-16 设计创作，主要内容包括：本发明公开了一种无水四丁基氟化铵的制备方法,其特征在于,包括以下步骤：将含水四丁基氟化铵溶解于有机溶剂中,通过分水器共沸带水30～180分钟,而后蒸去溶剂,再加入同等体积的相同溶剂,减压蒸馏,操作两次之后得到的固体加入THF,溶解后再减压除去溶剂,最后-10℃下冷却析出固体即为无水TBAF；本发明直接用已有的三水合四丁基氟化铵进行精制,通过有机溶剂进行共沸带水的方式进行除水,然后再在低温冷却结晶的方式得到目标产物无水四丁基氟化铵,解决了原有无水四丁基氟化铵制备过程中的复杂的工艺,生产成本低。(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.)

1. The 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 the solid, namely the anhydrous TBAF.

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 organic solvent is one of tetrahydrofuran, methyltetrahydrofuran, acetonitrile, dichloromethane and 1, 2-dichloroethane.

4. The method according to claim 3, wherein the method comprises the following steps: the organic solvent is 1, 2-dichloroethane or tetrahydrofuran.

5. The method according to claim 1, wherein the method comprises the following steps: the azeotropic entrainment of water was carried out under argon protection.

6. 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.

7. The method according to claim 1, wherein the method comprises the following steps: the resulting solid was drained and then stored as a THF solution.

8. 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%.

9. The method according to claim 1, wherein the method comprises 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, 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 to obtain 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 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 hydroscopic, usually in the form of a trihydrate, since fluoride ions are very strong hydrogen bond acceptors, water removal by simple distillation under reduced pressure, heating to 77 deg.C under high vacuum, β -dehydrogenation elimination occurs to form Hydrogen Fluoride (HF)₂ ^-) 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, and the method utilizes the nucleophilic substitution reaction of tetrabutylammonium cyanide and hexafluorobenzene at low temperature, prepares white solid by dropwise adding hexafluorobenzene at-65 ℃ and then reacting for four hours at-15 ℃, filters at-65 ℃ and washes by Tetrahydrofuran (THF), and the obtained anhydrous TBAF can be stored at-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:

the 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 30-60 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 the 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: