CN108439339B - Lithium borohydride LiB3H8Preparation method of (1) - Google Patents

Lithium borohydride LiB3H8Preparation method of (1) Download PDF

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CN108439339B
CN108439339B CN201810197304.XA CN201810197304A CN108439339B CN 108439339 B CN108439339 B CN 108439339B CN 201810197304 A CN201810197304 A CN 201810197304A CN 108439339 B CN108439339 B CN 108439339B
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lithium borohydride
lib
thf
lithium
borohydride
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CN108439339A (en
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陈学年
陈西孟
张絜
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Henan Normal University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B6/00—Hydrides of metals including fully or partially hydrided metals, alloys or intermetallic compounds ; Compounds containing at least one metal-hydrogen bond, e.g. (GeH3)2S, SiH GeH; Monoborane or diborane; Addition complexes thereof
    • C01B6/06—Hydrides of aluminium, gallium, indium, thallium, germanium, tin, lead, arsenic, antimony, bismuth or polonium; Monoborane; Diborane; Addition complexes thereof
    • C01B6/10—Monoborane; Diborane; Addition complexes thereof
    • C01B6/13—Addition complexes of monoborane or diborane, e.g. with phosphine, arsine or hydrazine
    • C01B6/15—Metal borohydrides; Addition complexes thereof
    • C01B6/19—Preparation from other compounds of boron
    • C01B6/21—Preparation of borohydrides of alkali metals, alkaline earth metals, magnesium or beryllium; Addition complexes thereof, e.g. LiBH4.2N2H4, NaB2H7
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/80—Compositional purity

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Abstract

The invention discloses a lithium borohydride lithium salt LiB3H8The preparation method ofAdding lithium borohydride into a reaction vessel under the anhydrous and oxygen-free conditions, and then adding B3H7Tetrahydrofuran solution THF. B3H7Stirring and reacting at-20-60 ℃ to obtain a pure target product, namely, lithium borohydride lithium salt LiB3H81.5 THF. The method has the advantages of simple operation, low toxicity, harmlessness, safety, reliability and suitability for large-scale production.

Description

Lithium borohydride LiB3H8Preparation method of (1)
Technical Field
The invention belongs to the technical field of preparation of borohydride, and particularly relates to a borohydride lithium salt LiB3H8The preparation method of (1).
Background
Negative ion B3H8 -Has attracted wide attention, mainly because of its higher hydrogen content, has very large application prospect in the field of hydrogen storage, such as the hydrogen storage material that has already been synthesized, contain a large amount of negative hydrogen; and has good solubility in common organic solvents, so the compound can be used as a reducing agent; and can be used as a precursor for synthesizing other boron-containing compounds, such as MgB semiconductor material2The precursor of (1).
B of metal cations and other non-metal cations due to limitations of the synthesis method3H8Borohydride compounds have not been well developed. Therefore, it is necessary to develop a synthetic method which is simple in operation, safe, nontoxic and low in cost.
Synthesis of M (B) at present3H8)nThe method for preparing the boron-like compound mainly comprises the following steps: 1. formation of NaB using diborane and an alkali metal, primarily sodium amalgam3H8In the method, mercury, diborane and the like which are high in toxicity and unsafe are used, the mercury has great harm to human bodies and is inconvenient to operate, and the diborane is extremely sensitive to air, flammable and explosive, has high toxicity and is also very dangerous to operate; 2. the elemental iodine oxidizes sodium borohydride at 100 ℃, the boiling point of the solvent required at the temperature is higher, energy is consumed, and the synthesized B3H8 -The negative ions contain indelible solvent; 3. solution of sodium amalgam and borane in tetrahydrofuran (THF. BH)3) Reaction, there are also disadvantages in the above-mentioned methods 1 and 2; 4. alkali metal sodium is dispersed on silica gel at 150 ℃, and then reacted with borane tetrahydrofuran,sodium is dispersed at the temperature, the operation is very inconvenient, and high danger exists; 5. dispersing sodium alkali metal on inorganic salt such as NaCl, CaCl under ball milling2Etc., there are also disadvantages in the above-mentioned method 4; 6. reaction of sodium-potassium alloy and borane in tetrahydrofuran to obtain KB3H8However, the sodium-potassium alloy is liquid, has much higher activity than sodium amalgam, is very flammable and explosive, and is not easy to operate.
Current lithium borohydride salts LiB3H8The synthesis method mainly uses lithium amalgam and THF-BH3The reaction is either LiBH4With THF. BH3The reaction is carried out under the reflux condition, the reaction time is long, the purification is difficult, and the yield is low. In view of the above synthesis B3H8The adverse factors of the boron-like hydride compound need to design a synthesis process which can avoid the use of dangerous drugs with high toxicity and has simple operation, safety and reliability3H8The preparation method of (1).
Disclosure of Invention
The technical problem to be solved by the invention is to provide a lithium borohydride lithium salt LiB which is simple to operate, safe, reliable, low in toxicity and harmless3H8The preparation method of (1).
The invention adopts the following technical scheme to solve the technical problems that the lithium borohydride lithium salt LiB3H8The preparation method is characterized by comprising the following specific steps: adding lithium borohydride into a reaction vessel under the anhydrous and oxygen-free conditions, and then adding B3H7Tetrahydrofuran solution THF. B3H7Stirring and reacting at-20-60 ℃ to obtain a pure target product, namely, lithium borohydride lithium salt LiB3H8·1.5THF。
More preferably, the lithium borohydride salt LiB3H8The preparation method is characterized by comprising the following specific steps: in a nitrogen glove box, filling lithium borohydride into a schlenk reaction bottle, sealing the schlenk reaction bottle by using a plug, removing the schlenk reaction bottle out of the glove box, and adding B with the molar concentration of 0.1-1 mol/L3H7Tetrahydrofuran solution THF. B3H7Wherein THF. B3H7The feeding molar ratio of the lithium borohydride to the lithium borohydride is 1: 1-4: 1, the mixture is stirred and reacted for 30-60 min at the temperature of-20-60 ℃, insoluble substances are removed through filtration, filtrate is concentrated, and a solvent is removed to obtain a pure viscous transparent liquid product LiB3H8·1.5THF。
The lithium borohydride lithium salt LiB of the invention3H8The reaction equation in the preparation method of (1) is:
LiBH4 + THF·B3H7 + 1.5 THF = LiB3H8·1.5THF + THF·BH3
compared with the prior art, the invention has the following beneficial effects: the method has the advantages of simple operation, low toxicity, harmlessness, safety, reliability and suitability for large-scale production.
Drawings
FIGS. 1 and 2 are lithium borohydride salts LiB prepared in example 1 of the present invention, respectively3H8In deuterated acetonitrile11B and1h liquid nuclear magnetic diagram, and the target product is pure LiB3H8·1.5THF。
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, 0.22g of lithium borohydride was added to a 500mL schlenk reaction flask containing magnetons, the schlenk reaction flask was removed from the glove box after sealing with a stopper, and 200mL of B with a molar concentration of 0.1mol/L was added3H7Tetrahydrofuran solution THF. B3H7Reacting at normal temperature for 60min, filtering to remove a small amount of insoluble substances, concentrating the filtrate to remove the solvent to obtain a viscous transparent liquid product LiB3H81.5THF, LiB obtained3H81.5THF weighed 1.28g, calculated yield 82%, which was checked by nuclear magnetic resonanceThe purity is close to 100%.
Example 2
All operations were performed under a nitrogen atmosphere. In a glove box, 0.22g of lithium borohydride was added to a 100mL schlenk reaction flask containing magnetons, the schlenk reaction flask was removed from the glove box after sealing with a stopper, and then 20mL of B with a molar concentration of 0.5mol/L was added3H7Tetrahydrofuran solution THF. B3H7Stirring and reacting at 0 ℃ for 40min, filtering to remove a small amount of insoluble substances, concentrating the filtrate to remove the solvent to obtain a viscous transparent liquid product LiB3H81.5THF, LiB obtained3H81.5THF weighed 1.31g, the calculated yield was 85%, and the purity was close to 100% by nuclear magnetic detection.
Example 3
All operations were performed under a nitrogen atmosphere. In a glove box, 0.22g of lithium borohydride was added to a 100mL schlenk reaction flask containing magnetons, the schlenk reaction flask was removed from the glove box after sealing with a stopper, and then 40mL of 1mol/L molar B was added3H7Tetrahydrofuran solution THF. B3H7Stirring and reacting at-20 ℃ for 30min, filtering to remove a small amount of insoluble substances, concentrating the filtrate to remove the solvent to obtain a viscous transparent liquid product LiB3H81.5THF, LiB obtained3H81.5THF weighed 1.30g, the calculated yield was 83%, and the purity was close to 100% by nuclear magnetic detection.
Example 4
All operations were performed under a nitrogen atmosphere. In a glove box, 0.22g of lithium borohydride was added to a 100mL schlenk reaction flask containing magnetons, the schlenk reaction flask was removed from the glove box after sealing with a stopper, and then 20mL of 1mol/L molar B was added3H7Tetrahydrofuran solution THF. B3H7Stirring and reacting at 60 ℃ for 30min, filtering to remove a small amount of insoluble substances, concentrating the filtrate to remove the solvent to obtain a viscous transparent liquid product LiB3H81.5THF, LiB obtained3H81.5THF weighed 1.33g, the calculated yield was 85%, and the purity was 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.

Claims (1)

1. Lithium borohydride LiB3H8The preparation method is characterized by comprising the following specific steps: adding lithium borohydride into a reaction vessel under the anhydrous and oxygen-free conditions, and then adding B3H7Tetrahydrofuran solution THF. B3H7Stirring and reacting at-20-60 ℃ to obtain a pure target product, namely, lithium borohydride lithium salt LiB3H8·1.5THF；
The method comprises the following specific steps: in a nitrogen glove box, filling lithium borohydride into a schlenk reaction bottle, sealing the schlenk reaction bottle by using a plug, removing the schlenk reaction bottle out of the glove box, and adding B with the molar concentration of 0.1-1 mol/L3H7Tetrahydrofuran solution THF. B3H7Wherein THF. B3H7The feeding molar ratio of the lithium borohydride to the lithium borohydride is 1: 1-4: 1, the mixture is stirred and reacted for 30-60 min at the temperature of-20-60 ℃, insoluble substances are removed through filtration, filtrate is concentrated, and a solvent is removed to obtain a pure viscous transparent liquid product LiB3H8·1.5THF。
CN201810197304.XA 2018-03-10 2018-03-10 Lithium borohydride LiB3H8Preparation method of (1) Expired - Fee Related CN108439339B (en)

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Citations (5)

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US7288236B2 (en) * 2003-01-22 2007-10-30 Chemetall Gmbh Process for the preparation of lithium borohydride
CN101896421A (en) * 2007-12-05 2010-11-24 新加坡国立大学 A hydrogen storage material and a process for release of hydrogen
CN105417496A (en) * 2014-09-23 2016-03-23 中国科学院大连化学物理研究所 synthesis method for borohydride of sodium
CN107416856A (en) * 2017-08-02 2017-12-01 河南师范大学 A kind of hydroboron [NH3BH2NH3]B3H8Synthetic method
CN107473184A (en) * 2017-08-02 2017-12-15 河南师范大学 A kind of hydroboron LiB of lithium3H8Synthetic method

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EP2470469A4 (en) * 2009-08-27 2015-04-22 Sigma Aldrich Co Llc Metal amidoborane compositions and processes for their preparation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7288236B2 (en) * 2003-01-22 2007-10-30 Chemetall Gmbh Process for the preparation of lithium borohydride
CN101896421A (en) * 2007-12-05 2010-11-24 新加坡国立大学 A hydrogen storage material and a process for release of hydrogen
CN105417496A (en) * 2014-09-23 2016-03-23 中国科学院大连化学物理研究所 synthesis method for borohydride of sodium
CN107416856A (en) * 2017-08-02 2017-12-01 河南师范大学 A kind of hydroboron [NH3BH2NH3]B3H8Synthetic method
CN107473184A (en) * 2017-08-02 2017-12-15 河南师范大学 A kind of hydroboron LiB of lithium3H8Synthetic method

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