阅读说明：本技术 一种硼氮氢化合物k[b3h7nh2bh2nh2b3h7]的合成方法 (Boron-nitrogen-hydrogen compound K [ B ]3H7NH2BH2NH2B3H7]Method of synthesis of ) 是由 陈西孟 贾斯涵 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氮氢化合物K[B-(3)H-(7)NH-(2)BH-(2)NH-(2)B-(3)H-(7)]的合成方法,属于硼氮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氢化钾加入到反应容器中,再加入NH-(3)B-(3)H-(7)的四氢呋喃溶液,于-40～50℃搅拌反应制得目标产物硼氮氢化合物K[B-(3)H-(7)NH-(2)BH-(2)NH-(2)B-(3)H-(7)]。本发明提供的合成方法操作简单,安全高效,适合规模化生产,为其进一步的性能研究打下了基础。(The invention discloses a boron-nitrogen-hydrogen compound K [ B ] 3 H 7 NH 2 BH 2 NH 2 B 3 H 7 ]Belonging to the technical field of synthesis of boron-nitrogen-hydrogen compounds. The technical scheme provided by the invention has the key points that: adding potassium hydride into a reaction vessel under the anhydrous and oxygen-free conditions, and then adding NH 3 B 3 H 7 Stirring the tetrahydrofuran solution at-40-50 deg.c to react to obtain target product boron-nitrogen-hydrogen compound K [ B ] 3 H 7 NH 2 BH 2 NH 2 B 3 H 7 ]. The synthesis method provided by the invention is simple to operate, safe and efficient, is suitable for large-scale production, and lays a foundation for further performance research.)

1. Boron-nitrogen-hydrogen compound K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]The synthesis method is characterized by comprising the following specific processes: adding potassium hydride into a reaction vessel under the anhydrous and oxygen-free conditions, and then adding NH₃B₃H₇Stirring the tetrahydrofuran solution at-40-50 deg.c to react to obtain target product boron-nitrogen-hydrogen compound K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]。

2. The boron-nitrogen-hydrogen compound K [ B ] according to claim 1₃H₇NH₂BH₂NH₂B₃H₇]The synthesis method is characterized by comprising the following specific steps: in a nitrogen glove box, hydrogen is addedThe potassium solution was filled into a schlenk reaction flask, the schlenk reaction flask was sealed with a stopper, the glove box was removed, and NH was added₃B₃H₇The tetrahydrofuran solution of (1), wherein potassium hydride and NH₃B₃H₇The molar ratio of the raw materials is 1: 1-1: 4, the mixture is stirred and reacted for 12-36 hours at the temperature of-40-50 ℃ until the reaction is finished, insoluble substances are removed by filtration, filtrate is concentrated to remove solvent to obtain white viscous solid, the white viscous solid is washed for a plurality of times by methylbenzene, and then the white pure boron-nitrogen-hydrogen compound K [ B ] is obtained by removing the solvent by vacuum concentration₃H₇NH₂BH₂NH₂B₃H₇]And (3) powder.

3. The boron-nitrogen-hydrogen compound K [ B ] according to claim 1 or 2₃H₇NH₂BH₂NH₂B₃H₇]The synthesis method is characterized in that: the reaction temperature in the synthesis process is preferably room temperature, and potassium hydride and NH are added₃B₃H₇The feeding molar ratio of (3) is preferably 1:2, and the stirring reaction time is preferably 24 h.

Technical Field

The invention belongs to the technical field of synthesis of boron-nitrogen-hydrogen compounds, and particularly relates to a boron-nitrogen-hydrogen compound KB₃H₇NH₂BH₂NH₂B₃H₇]The method of (1).

Background

Boron-nitrogen-hydrogen compound has wide applicationDue to its high hydrogen content, it has very great application prospect in the field of hydrogen storage, such as synthesized hydrogen storage material NH₄[B₃H₈]And NH₃B₃H₇Etc. (J. Am. Chem. Soc. 2009, 131, 855-864;Inorg. Chem. 2011, 50, 3738-3742). Meanwhile, the compound contains a large amount of negative hydrogen, has certain reducibility and good solubility in common organic solvents, and therefore can be used as a reducing agent in different solvents. The compound can also be used as a precursor for synthesizing other boron-containing compounds, such as MgB which is a semiconductor material₂Precursor of Mg (B)₃H₈)₂Precursor NH for synthesizing inorganic material BN₃BH₃And the like. Recent studies have shown that alkali metal salts of boron-nitrogen-hydrogen compounds can act as solid ion conductors and exhibit higher ion conductivity properties. Therefore, the synthesis of the novel boron-nitrogen-hydrogen compound is an important link for researching the compound.

Among boron nitrogen hydride compounds, compounds having a ternary B ring are a very important class of compounds among them. The vast majority of ternary B-ring compounds are synthesized as alkali metal salts MB₃H₈Is the starting material. Currently synthesized alkali metal salt MB₃H₈The method mainly comprises the following steps: 1) formation of NaB using diborane and an alkali metal, primarily sodium amalgam₃H₈(ii) a 2) Oxidizing sodium borohydride by elemental iodine at 100 ℃; 3) sodium amalgam and borane in tetrahydrofuran (THF. BH)₃) Carrying out reaction; 4) dispersing sodium alkali metal on silica gel at 150 ℃, and then reacting with tetrahydrofuran of borane; 5) dispersing sodium alkali metal on inorganic salt such as NaCl, CaCl under ball milling₂And the like. The synthesis method based on the above enables MB₃H₈Can be synthesized in large quantity, and can be used as a starting material to synthesize ammonia borane NH with a ternary B structure₃B₃H₇。

It is known from the literature that there is no NH at present₃B₃H₇Research on derivatives, i.e. synthesis and related performance studies without novel derivatives thereofAnd (6) obtaining the finished product. Based on this, it is necessary to design a method for NH₃B₃H₇The designed synthesis method is simple and efficient, a solid foundation is laid for the performance research of the boron nitrogen hydrogen compound, and the research of boron chemistry is further enriched.

Disclosure of Invention

The technical problem solved by the invention is to provide a boron nitrogen hydrogen compound K [ B ] with simple operation, safety and reliability and higher yield₃H₇NH₂BH₂NH₂B₃H₇]The method of (1).

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

boron-nitrogen-hydrogen compound K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]The synthesis method is characterized by comprising the following specific processes: adding potassium hydride into a reaction vessel under the anhydrous and oxygen-free conditions, and then adding NH₃B₃H₇Stirring the tetrahydrofuran solution at-40-50 deg.c to react to obtain target product boron-nitrogen-hydrogen compound K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]。

The boron-nitrogen-hydrogen compound K [ B ] of the invention₃H₇NH₂BH₂NH₂B₃H₇]The synthesis method is characterized by comprising the following specific steps: in a nitrogen glove box, potassium hydride was charged into a schlenk reaction flask, the schlenk reaction flask was removed from the glove box after sealing with a stopper, and NH was added₃B₃H₇The tetrahydrofuran solution of (1), wherein potassium hydride and NH₃B₃H₇The molar ratio of the raw materials is 1: 1-1: 4, the mixture is stirred and reacted for 12-36 hours at the temperature of-40-50 ℃ until the reaction is finished, insoluble substances are removed by filtration, filtrate is concentrated to remove solvent to obtain white viscous solid, the white viscous solid is washed for a plurality of times by methylbenzene, and then the white pure boron-nitrogen-hydrogen compound K [ B ] is obtained by removing the solvent by vacuum concentration₃H₇NH₂BH₂NH₂B₃H₇]And (3) powder.

Further preferably, it is synthesizedThe reaction temperature is preferably room temperature, potassium hydride and NH₃B₃H₇The feeding molar ratio of (3) is preferably 1:2, and the stirring reaction time is preferably 24 h.

The present invention provides a novel boron-nitrogen-hydrogen compound K [ B₃H₇NH₂BH₂NH₂B₃H₇]The synthesis method is simple to operate, safe and efficient, is suitable for large-scale production, and lays a foundation for further performance research.

Drawings

FIG. 1 shows a boron-nitrogen-hydrogen compound K [ B ] synthesized in example 1 of the present invention₃H₇NH₂BH₂NH₂B₃H₇]In deuterated acetonitrile¹¹B and¹¹B{¹h liquid nuclear magnetic diagram, the target product is pure K B₃H₇NH₂BH₂NH₂B₃H₇]。

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, 0.40 g of potassium hydride was added to a 100 mL schlenk reaction flask containing magnetons, and the schlenk reaction flask was removed from the glove box after sealing with a stopper; then adding NH₃B₃H₇40 mL of tetrahydrofuran solution (0.57 g of NH dissolved therein)₃B₃H₇) Stirring and reacting for 36 h at 50 ℃; filtering to remove insoluble substances, concentrating the filtrate to remove solvent to obtain white viscous solid, washing the solid with toluene for 3 times (each time 20 mL), and vacuum concentrating to remove solvent to obtain white solid product, i.e. pure K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]And (3) powder. Calculating the resulting K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]The yield of (A) is 65%, and the purity of the product is close to 100% by nuclear magnetic detection.

Example 2

All operations were performed under a nitrogen atmosphere. In a glove box, 0.40 g of potassium hydride was added to a 100 mL schlenk reaction flask containing magnetons, and the schlenk reaction flask was removed from the glove box after sealing with a stopper; then adding NH₃B₃H₇40 mL of tetrahydrofuran solution (0.114 g of NH dissolved therein)₃B₃H₇) Stirring and reacting for 24 hours at 25 ℃; filtering to remove insoluble substances, concentrating the filtrate to remove solvent to obtain white viscous solid, washing the solid with toluene for 3 times (each time 20 mL), and vacuum concentrating to remove solvent to obtain white solid product, i.e. pure K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]And (3) powder. Calculating the resulting K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]The yield of (A) is 91%, and the purity of the product is close to 100% by nuclear magnetic detection.

Example 3

All operations were performed under a nitrogen atmosphere. In a glove box, 0.40 g of potassium hydride was added to a 100 mL schlenk reaction flask containing magnetons, and the schlenk reaction flask was removed from the glove box after sealing with a stopper; then adding NH₃B₃H₇40 mL of tetrahydrofuran solution (1.71 g of NH dissolved therein)₃B₃H₇) Stirring and reacting for 18 h at the temperature of 0 ℃; filtering to remove insoluble substances, concentrating the filtrate to remove solvent to obtain white viscous solid, washing the solid with toluene for 3 times (each time 20 mL), and vacuum concentrating to remove solvent to obtain white solid product, i.e. pure K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]And (3) powder. Calculating the resulting K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]The yield of (A) is 72%, and the purity of the product is close to 100% by nuclear magnetic detection.

Example 4

All operations were performed under a nitrogen atmosphere. In glove box, suitA 100 mL schlenk flask with magnetons was charged with 0.40 g of potassium hydride and after sealing with a stopper, the schlenk flask was removed from the glove box; then NH is added₃B₃H₇40 mL of tetrahydrofuran solution (2.28 g of NH dissolved therein)₃B₃H₇) Stirring and reacting for 12 hours at the temperature of minus 40 ℃; filtering to remove insoluble substances, concentrating the filtrate to remove solvent to obtain white viscous solid, washing the solid with toluene for 3 times (each time 20 mL), and vacuum concentrating to remove solvent to obtain white solid product, i.e. pure K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]And (3) powder. Calculating the resulting K [ B ]₃H₇NH₂BH₂NH₂B₃H₇]The yield of (A) is 79%, and the purity of the product 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.