CN108439339A - A kind of hydroboron lithium salts LiB3H8Preparation method - Google Patents

A kind of hydroboron lithium salts LiB3H8Preparation method Download PDF

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Publication number
CN108439339A
CN108439339A CN201810197304.XA CN201810197304A CN108439339A CN 108439339 A CN108439339 A CN 108439339A CN 201810197304 A CN201810197304 A CN 201810197304A CN 108439339 A CN108439339 A CN 108439339A
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lib
hydroboron
lithium salts
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thfb
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CN108439339B (en
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陈学年
陈西孟
张絜
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Henan Normal University
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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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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Abstract

The invention discloses a kind of hydroboron lithium salts LiB3H8Preparation method, lithium borohydride is added in reaction vessel under conditions of anhydrous and oxygen-free, B is then added3H7Tetrahydrofuran solution THFB3H7, obtained pure target product hydroboron lithium salts LiB is stirred to react in 20~60 DEG C3H8·1.5THF.The present invention is easy to operate, and low toxicity is harmless, securely and reliably, is suitble to large-scale production.

Description

A kind of hydroboron lithium salts LiB3H8Preparation method
Technical field
The invention belongs to the preparing technical fields of hydroboron, and in particular to a kind of hydroboron lithium salts LiB3H8's Preparation method.
Background technology
Anion B3H8 -Extensive concern is caused, mainly due to its higher hydrogen content, is had in hydrogen storage field Very big application prospect, the hydrogen storage material such as synthesized contain largely negative hydrogen；And have in common organic solvent Good dissolubility, therefore can be used as reducing agent；And it can be as the predecessor for synthesizing other boron-containing compounds, such as Synthesize semi-conducting material MgB2Predecessor.
Due to the limitation of synthetic method, the B of metal cation class and other non-metal cations classes3H8Hydroboron Do not developed well.Therefore, developing that a kind of easy to operate, safe and non-toxic and low-cost synthetic method has very much must It wants.
M (B are just synthesized at present3H8)nThe method of class hydroboron mainly has：1, using diborane and alkali metal, mainly Sodium amalgam generates NaB3H8, used very big toxicity and extremely unsafe mercury, diborane etc. in method, mercury to the harm of human body very Greatly, and inconvenient, diborane is extremely sensitive to air, inflammable and explosive, and with severe toxicity, operates same abnormally dangerous；2, single Matter iodine aoxidizes sodium borohydride at 100 DEG C, and required solvent boiling point is higher at a temperature of this, consuming energy, and the B synthesized3H8 -Bear from Son is containing except the solvent not fallen；3, the tetrahydrofuran solution of sodium amalgam and borine（THF·BH3）Reaction, equally exists above-mentioned side Disadvantage in method 1 and 2；4, alkali metallic sodium is dispersed on silica gel at 150 DEG C, is then reacted with the tetrahydrofuran of borine, herein At a temperature of disperse sodium, operation is very inconvenient, and with the presence of very high dangerous；5, alkali metallic sodium is dispersed under conditions of ball milling On inorganic salts, such as NaCl, CaCl2Deng equally existing the disadvantage in the above method 4；6, the tetrahydrofuran of Na-K alloy and borine KB is obtained by the reaction3H8, but Na-K alloy is liquid, and it is more much higher than the activity of sodium amalgam, it is highly combustible explosive, is not easy to grasp very much Make.
Hydroboron lithium salts LiB at present3H8Synthetic method mainly use lithium amalgam and THFBH3Reaction is either LiBH4With THFBH3It reacts under reflux conditions, the reaction time is long, purification difficult, low yield.In view of the above synthesis B3H8Class The unfavorable factor of hydroboron, it is necessary to designing a kind of building-up process can avoid using the high hazardous chemical of toxicity, and Hydroboron lithium salts LiB easy to operate, safe and reliable3H8Preparation method.
Invention content
The technical problem to be solved by the present invention is to provide a kind of easy to operate, safe and reliable and less toxic harmless hydroboration conjunctions Object lithium salts LiB3H8Preparation method.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, a kind of hydroboron lithium salts LiB3H8System Preparation Method, it is characterised in that detailed process is：Lithium borohydride is added in reaction vessel under conditions of anhydrous and oxygen-free, then B is added3H7Tetrahydrofuran solution THFB3H7, it is stirred to react obtained pure target product hydroboration in -20~60 DEG C and closes Object lithium salts LiB3H8·1.5THF。
Further preferably, the hydroboron lithium salts LiB3H8Preparation method, it is characterised in that the specific steps are： In nitrogen glove box, lithium borohydride is fitted into schlenk reaction bulbs, is removed schlenk reaction bulbs with after plug seal Then the B that molar concentration is 0.1~1mol/L is added in glove box3H7Tetrahydrofuran solution THFB3H7, wherein THFB3H7 Molar ratio with lithium borohydride is 1:1~4:1, it is stirred to react 30~60min in -20~60 DEG C, is filtered to remove insoluble matter, Filtrate is concentrated into removing solvent and obtains pure thick transparency liquid product LiB3H8·1.5THF。
Hydroboron lithium salts LiB of the present invention3H8Preparation method in reaction equation be：
LiBH4 + THF·B3H7 + 1.5 THF = LiB3H8·1.5THF + THF·BH3
The present invention has the advantages that compared with prior art：The present invention is easy to operate, and low toxicity is harmless, securely and reliably, fits Close large-scale production.
Description of the drawings
Fig. 1 and Fig. 2 is hydroboron lithium salts LiB made from the embodiment of the present invention 1 respectively3H8In deuterated acetonitrile11B With1H liquid core magnetic charts, target product obtained is pure LiB as seen from the figure3H8·1.5THF。
Specific implementation mode
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on the above of the present invention belong to this hair Bright range.
Embodiment 1
All operations carry out in a nitrogen atmosphere.In glove box, into the schlenk reaction bulbs of the 500mL equipped with magneton 0.22g lithium borohydrides are added, schlenk reaction bulbs are removed into glove box with after plug seal, 200mL molar concentrations are then added For the B of 0.1mol/L3H7Tetrahydrofuran solution THFB3H7, 60 min are reacted under normal temperature condition, are filtered to remove on a small quantity not Filtrate is concentrated removing solvent and obtains thick transparency liquid product LiB by molten object3H81.5THF, obtained LiB3H8· 1.5THF is weighed as 1.28g, and it is 82% to calculate yield, and nuclear-magnetism detects its purity close to 100%.
Embodiment 2
All operations carry out in a nitrogen atmosphere.In glove box, into the schlenk reaction bulbs of the 100mL equipped with magneton 0.22g lithium borohydrides are added, schlenk reaction bulbs are removed into glove box with after plug seal, 20mL molar concentrations are then added For the B of 0.5mol/L3H7Tetrahydrofuran solution THFB3H7, it is stirred to react 40min in 0 DEG C, is filtered to remove a small amount of insoluble matter, Filtrate is concentrated into removing solvent and obtains thick transparency liquid product LiB3H81.5THF, obtained LiB3H8·1.5THF It is weighed as 1.31g, it is 85% to calculate yield, and nuclear-magnetism detects its purity close to 100%.
Embodiment 3
All operations carry out in a nitrogen atmosphere.In glove box, into the schlenk reaction bulbs of the 100mL equipped with magneton 0.22g lithium borohydrides are added, schlenk reaction bulbs are removed into glove box with after plug seal, 40mL molar concentrations are then added For the B of 1mol/L3H7Tetrahydrofuran solution THFB3H7, it is stirred to react 30min in -20 DEG C, is filtered to remove a small amount of insoluble matter, Filtrate is concentrated into removing solvent and obtains thick transparency liquid product LiB3H81.5THF, obtained LiB3H8·1.5THF It is weighed as 1.30g, it is 83% to calculate yield, and nuclear-magnetism detects its purity close to 100%.
Embodiment 4
All operations carry out in a nitrogen atmosphere.In glove box, into the schlenk reaction bulbs of the 100mL equipped with magneton 0.22g lithium borohydrides are added, schlenk reaction bulbs are removed into glove box with after plug seal, 20mL molar concentrations are then added For the B of 1mol/L3H7Tetrahydrofuran solution THFB3H7, it is stirred to react 30min in 60 DEG C, is filtered to remove a small amount of insoluble matter, Filtrate is concentrated into removing solvent and obtains thick transparency liquid product LiB3H81.5THF, obtained LiB3H8·1.5THF It is weighed as 1.33g, it is 85% to calculate yield, and nuclear-magnetism detects its purity close to 100%.
Embodiment above describes the basic principles and main features and advantage of the present invention, and the technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe the originals of the present invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (2)

1. a kind of hydroboron lithium salts LiB3H8Preparation method, it is characterised in that detailed process is：In the condition of anhydrous and oxygen-free It is lower that lithium borohydride is added in reaction vessel, B is then added3H7Tetrahydrofuran solution THFB3H7, stirred in -20~60 DEG C Mix the target product hydroboron lithium salts LiB that reaction is made pure3H8·1.5THF。
2. hydroboron lithium salts LiB according to claim 13H8Preparation method, it is characterised in that the specific steps are： In nitrogen glove box, lithium borohydride is fitted into schlenk reaction bulbs, is removed schlenk reaction bulbs with after plug seal Then the B that molar concentration is 0.1~1mol/L is added in glove box3H7Tetrahydrofuran solution THFB3H7, wherein THFB3H7 Molar ratio with lithium borohydride is 1:1~4:1, it is stirred to react 30~60min in -20~60 DEG C, is filtered to remove insoluble matter, Filtrate is concentrated into removing solvent and obtains pure thick transparency 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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113526466A (en) * 2021-08-31 2021-10-22 河南师范大学 Potassium salt KB of boron hydride11H14Method of synthesis of

Citations (6)

* 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
US20120301382A1 (en) * 2009-08-27 2012-11-29 Sigma Aldrich Co. Llc Metal amidoborane compositions and processes for their preparation
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

Patent Citations (6)

* 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
US20120301382A1 (en) * 2009-08-27 2012-11-29 Sigma Aldrich Co. Llc Metal amidoborane compositions and processes for their preparation
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

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113526466A (en) * 2021-08-31 2021-10-22 河南师范大学 Potassium salt KB of boron hydride11H14Method of synthesis of
CN113526466B (en) * 2021-08-31 2023-11-17 河南师范大学 Boron hydrogen compound potassium salt KB 11 H 14 Is synthesized by the method of (2)

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