阅读说明：本技术 一种硼氢化合物钾盐kb11h14的合成方法 (Potassium salt KB of boron hydride11H14Method of synthesis of ) 是由 陈西孟 荆怡 王红菊 陈学年 于 2021-08-31 设计创作，主要内容包括：本发明公开了一种硼氢化合物钾盐KB-(11)H-(14)的合成方法,属于硼氢化合物的合成技术领域。本发明的技术方案要点为：在无水无氧的条件下将硼氢化钾加入到反应容器中,再加入二甲基硫醚硼烷的1,4-二氧六环溶液,于25-90℃搅拌反应制得目标产物硼氢化合物钾盐KB-(11)H-(14)。本发明操作简单,低毒无害,安全可靠,成本低廉,适合规模化生产。(The invention discloses a boron hydride potassium salt KB 11 H 14 Belonging to the technical field of synthesis of boron hydride compounds. The technical scheme provided by the invention has the key points that: adding potassium borohydride into a reaction vessel under the anhydrous and oxygen-free conditions, adding a 1, 4-dioxane solution of dimethyl sulfide borane, and stirring and reacting at 25-90 ℃ to obtain a target product, namely, potassium borohydride salt KB 11 H 14 . The method has the advantages of simple operation, low toxicity, harmlessness, safety, reliability and low cost, and is suitable for large-scale production.)

1. Potassium salt KB of boron hydride₁₁H₁₄The synthesis method is characterized by comprising the following specific processes: adding potassium borohydride into a reaction vessel under the anhydrous and oxygen-free conditions, and then adding dimethyl sulfide borane DMS & BH₃The 1, 4-dioxane solution is stirred and reacted at the temperature of 25-90 ℃ to prepare a target product, namely a boron hydride potassium salt KB₁₁H₁₄。

2. The potassium borohydride salt KB as defined in claim 1₁₁H₁₄The synthesis method is characterized by comprising the following specific steps: in a nitrogen glove box, adding KBH of potassium borohydride₄Loading into a schlenk reaction flask, sealing with a plug, removing the schlenk reaction flask from the glove box, and adding dimethyl sulfide borane DMS & BH with a molar concentration of 1.0 mol/L₃The feeding molar ratio of potassium borohydride to dimethyl sulfide borane is 1:5-1:16, the reaction is carried out for 12-36 h at the temperature of 25-90 ℃, a small amount of insoluble substances are removed by filtration, the filtrate is concentrated to remove the solvent, and a white solid product KB is obtained₁₁H₁₄。

3. The potassium borohydride salt KB as defined in claim 1 or claim 2₁₁H₁₄The synthesis method is characterized in that: the potassium borohydrideThe feeding molar ratio of the dimethyl sulfide borane to the dimethyl sulfide borane is preferably 1:10, the reaction temperature of the synthesis process is preferably 75 ℃, and the reaction time is preferably 24 hours.

Technical Field

The invention belongs to the technical field of synthesis of borohydride, and particularly relates to a borohydride potassium salt KB₁₁H₁₄The method of (1).

Background

Anion B having polyhedral structure₁₁H₁₄ ^-Due to its wide use, great interest has been drawn to its ability to be oxidized to form B₁₀H₁₄And further converted into carborane, which has a very wide use in the military industry field. Via negative ions B₁₁H₁₄ ^-The synthesis of carborane is one of the most efficient methods known at present. In addition, corresponding anions B₁₁H₁₄ ^-The alkali metal salt of (a) can also be used as a solid ion conductor, which is newly developed in recent years and has good conductivity, and provides a solution to the disadvantages of liquid electrolytes. However, due to limitations of the synthetic method, the anion B₁₁H₁₄ ^-Alkali metal salts and their derivatives have not been well developed. Therefore, it is necessary and significant to design a synthetic method which is simple in operation, safe, nontoxic and low in cost.

In previous synthetic methods, there are generally several disadvantages: 1) most of the synthesis methods involve the use of diborane, which is a flammable and explosive toxic gas, and the safety problem is very easy to occur in the use process; 2) expensive reagents such as tris-pentafluorophenyl borane are generally used in addition to diborane, which significantly increases the cost of synthesis and is not suitable for large-scale synthesis; 3) the synthesis process needs higher reaction temperature (150-; 4) the conditions required by the reaction per se make the reaction process difficult to control, cause the generated product to be mixed with various other borane compounds, increase the difficulty of separation and purification and further cause lower yield.

Therefore, in order to be able to continue the development of the negative ions B₁₁H₁₄ ^-The related research and large-scale practical application of the method needs to design the negative ion B with controllable synthesis process, simple operation, low cost, safety and reliability₁₁H₁₄ ^-A method for synthesizing salt.

Disclosure of Invention

The invention solves the technical problem of providing the potassium borohydride KB salt which is simple to operate, safe, reliable and low in cost₁₁H₁₄The method of (1).

The invention adopts the following technical scheme for solving the technical problems:

potassium salt KB of boron hydride₁₁H₁₄Is characterized in thatThe specific process is as follows: adding potassium borohydride into a reaction vessel under the anhydrous and oxygen-free conditions, and then adding dimethyl sulfide borane (DMS & BH)₃) The 1, 4-dioxane solution is stirred and reacted at the temperature of 25-90 ℃ to prepare a target product, namely a boron hydride potassium salt KB₁₁H₁₄。

Potassium salt KB of boron hydride according to the invention₁₁H₁₄The synthesis method is characterized by comprising the following specific steps: in a nitrogen glove box, potassium borohydride (KBH)₄) Filling into a schlenk reaction bottle, sealing with a plug, removing the schlenk reaction bottle from the glove box, and adding dimethyl sulfide borane (DMS & BH) with a molar concentration of 1.0 mol/L₃) The feeding molar ratio of potassium borohydride to dimethyl sulfide borane is 1:5-1:16, the reaction is carried out for 12-36 h at the temperature of 25-90 ℃, a small amount of insoluble substances are removed by filtration, the filtrate is concentrated to remove the solvent, and a white solid product KB is obtained₁₁H₁₄。

Further preferably, the feeding molar ratio of the potassium borohydride to the dimethyl sulfide borane is preferably 1:10, the reaction temperature in the synthesis process is preferably 75 ℃, and the reaction time is preferably 24 h.

The potassium borohydride salt KB of the invention₁₁H₁₄The reaction equation in the synthesis method of (1) is:

KBH₄ + 10 DMS·BH₃ = KB₁₁H₁₄ + 10 H₂ + 10 DMS

compared with the prior art, the invention has the following advantages and beneficial effects: the method has the advantages of simple operation, low toxicity, harmlessness, safety, reliability and low cost, and is suitable for large-scale production.

Drawings

FIG. 1 is the potassium borohydride salt KB synthesized in example 1 of the present invention₁₁H₁₄In deuterated acetonitrile¹¹B and¹¹B{¹h } liquid nuclear magnetic diagram, and the target product is pure KB₁₁H₁₄。

Detailed Description

The present invention is described in further detail below with reference to examples, but it should not be construed that the scope of the above subject matter of the present invention is limited to the following examples, and that all the technologies realized based on the above subject matter of the present invention belong to the scope of the present invention.

Example 1

All operations were performed under a nitrogen atmosphere. In a glove box, 0.54 g of potassium borohydride was added to a 200 mL schlenk reaction flask containing magnetons, and the schlenk reaction flask was removed from the glove box after sealing with a stopper; then 50 mL of DMS & BH with the molar concentration of 1.0 mol/L is added₃Reacting the 1, 4-dioxane solution at 90 ℃ for 12 hours; filtering to remove a small amount of insoluble substances, concentrating the filtrate to remove the solvent to obtain white solid product KB₁₁H₁₄The calculated yield is 43%, and the purity is close to 100% by nuclear magnetic detection.

Example 2

All operations were performed under a nitrogen atmosphere. In a glove box, 0.54 g of potassium borohydride was added to a 200 mL schlenk reaction flask containing magnetons, and the schlenk reaction flask was removed from the glove box after sealing with a stopper; then 100 mL of DMS & BH with the molar concentration of 1.0 mol/L is added₃Reacting the 1, 4-dioxane solution at 75 ℃ for 24 hours; filtering to remove a small amount of insoluble substances, concentrating the filtrate to remove the solvent to obtain white solid product KB₁₁H₁₄The calculated yield is 92%, and the purity is close to 100% by nuclear magnetic detection.

Example 3

All operations were performed under a nitrogen atmosphere. In a glove box, 0.54 g of potassium borohydride was added to a 200 mL schlenk reaction flask containing magnetons, and the schlenk reaction flask was removed from the glove box after sealing with a stopper; then 120 mL of DMS & BH with the molar concentration of 1.0 mol/L is added₃Reacting the 1, 4-dioxane solution at 55 ℃ for 30 hours; filtering to remove a small amount of insoluble substances, concentrating the filtrate to remove the solvent to obtain white solid product KB₁₁H₁₄The calculated yield is 81%, and the purity is close to 100% by nuclear magnetic detection.

Example 4

All operations were performed under a nitrogen atmosphere. In a glove box, 0.54 g of potassium borohydride was added to a 200 mL schlenk reaction flask containing magnetons, and the schlenk reaction flask was sealed with a stopper and thenMoving out the glove box; 160 mL of DMS & BH with the molar concentration of 1.0 mol/L are added₃Reacting the 1, 4-dioxane solution at 25 ℃ for 36 hours; filtering to remove a small amount of insoluble substances, concentrating the filtrate to remove the solvent to obtain white solid product KB₁₁H₁₄The calculated yield is 26%, and the purity is close to 100% by nuclear magnetic detection.

The foregoing embodiments illustrate the principles, principal features and advantages of the invention, and it will be understood by those skilled in the art that the invention is not limited to the foregoing embodiments, which are merely illustrative of the principles of the invention, and that various changes and modifications may be made therein without departing from the scope of the principles of the invention.