CN114907391A - Method for synthesizing borane compound ethylenediamine diethylborane - Google Patents
Method for synthesizing borane compound ethylenediamine diethylborane Download PDFInfo
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- CN114907391A CN114907391A CN202210336705.5A CN202210336705A CN114907391A CN 114907391 A CN114907391 A CN 114907391A CN 202210336705 A CN202210336705 A CN 202210336705A CN 114907391 A CN114907391 A CN 114907391A
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- borane
- ethylenediamine
- diethylborane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses a synthesis method of a borane compound, namely ethylenediamine-diethylborane, and belongs to the technical field of synthesis of borane compounds. The technical scheme provided by the invention has the key points that: reacting ethanediamine borane BH under anhydrous and oxygen-free conditions 3 NH 2 CH 2 CH 2 NH 2 BH 3 Adding into a reaction vessel, and then adding tetrahydrofuran borane complex THF-BH 3 Stirring the tetrahydrofuran solution at the temperature of between 25 and 65 ℃ to react to obtain a target product borane compound, namely ethylenediamine-diethylborane B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 . The synthesis method provided by the invention is simple to operate, safe and efficient, and lays a foundation for further performance research.
Description
Technical Field
The invention belongs to the technical field of synthesis of borane compounds, and particularly relates to a borane compound ethylenediamine-diethylborane (B) 2 H 5 NHCH 2 CH 2 NHB 2 H 5 ) The method of (1).
Background
The borane is a boron-containing compound with B-H bond and is widely applied toEnergy storage materials, organic synthesis, catalysis and the like. The study of boranes has been in the last century, during which a large number of boranes have been synthesized. The most of the synthesized borane compounds are Lewis acid-base addition type compounds, for example, NH, due to the electron deficiency of the B atom 3 BH 3 、NaBH 3 NH 2 BH 3 、(CH 3 )SBH 3 And the like borane compounds. Compounds containing atoms such as N, O, P, S, which are capable of providing lone pair electrons to coordinate with B, are the preferred ligands for the synthesis of borane-based compounds. Among these compounds, N-containing boranes have been studied most and B/N chain compounds (NH) have been synthesized at present 3 BH 3 、NH 3 BH 2 NH 2 BH 3 、NH 3 BH 2 NH 2 BH 2 NH 2 BH 3 、NH 2 B 2 H 5 ) And their substituted analogs, inorganic salt type B/N chain compounds (NaNH) 2 BH 3 、Na[BH 3 NH 2 BH 3 ]、Na[BH 3 NH 2 BH 2 NH 2 BH 3 ]、Na[BH(NH 2 BH 3 ) 3 ]) And the like. Borane compounds containing O and P have also been studied in part, e.g., C 4 H 8 OBH 3 、PH 3 BH 3 Pinacolborane, and the like, which are mainly applied to the field of organic chemical synthesis.
In addition to the above-mentioned boranes, there is a class of organic-inorganic hybrid boranes, which are currently under less research. In view of the wide application of the borane compounds, it is necessary to design a novel organic-inorganic hybrid borane compound, and the designed synthetic method is relatively simple and efficient, so as to lay a solid foundation for the application research of the borane compound and further enrich the research of boron chemistry.
Disclosure of Invention
The invention solves the technical problem of providing a method for synthesizing the borane compound ethylenediamine diethylborane, which has the advantages of simple operation, safety, reliability and higher yield.
The present invention is to solve the above-mentioned technologyThe technical scheme is characterized in that the method for synthesizing the borane compound ethylenediamine diethylborane is characterized by comprising the following steps of: under the condition of no water and no oxygen, ethylenediamine borane BH is added 3 NH 2 CH 2 CH 2 NH 2 BH 3 Adding into a reaction vessel, and adding tetrahydrofuran borane complex THF-BH 3 Stirring the tetrahydrofuran solution at 25-65 ℃ to react to obtain a target product borane compound ethylenediamine-diethylborane B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 。
Further preferably, the synthesis method of the borane compound ethylenediamine diethylborane is characterized by comprising the following specific steps: in a nitrogen glove box, ethylenediamine borane BH 3 NH 2 CH 2 CH 2 NH 2 BH 3 Placing into a schlenk reaction flask, sealing with a stopper, removing the schlenk reaction flask from the glove box, and adding 1mol/L tetrahydrofuran borane complex THF. BH 3 In a solution of tetrahydrofuran of (4), wherein BH 3 NH 2 CH 2 CH 2 NH 2 BH 3 And THF. BH 3 The feeding molar ratio of the raw materials is 1: 2-1: 6, the raw materials are stirred and reacted for 12-36 hours at the temperature of 25-65 ℃, precipitates are filtered after the reaction is finished, filtrate is reserved, tetrahydrofuran solution in the filtrate is evaporated in a rotating mode to obtain a viscous product, namely the target product borane compound ethylenediamine diethylborane B with the purity close to 100 percent 2 H 5 NHCH 2 CH 2 NHB 2 H 5 。
Further preferably, the stirring reaction temperature in the synthesis process is 50 ℃, and BH is 3 NH 2 CH 2 CH 2 NH 2 BH 3 And THF. BH 3 The feeding molar ratio of (1) to (4) and the stirring reaction time of 24 hours.
The reaction equation in the synthesis method of the borane compound ethylenediamine diethylborane is as follows:
BH 3 NH 2 CH 2 CH 2 NH 2 BH 3 + 2 THF·BH 3 = B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 + 2 H 2 + 2 THF。
compared with the prior art, the invention has the following advantages and beneficial effects: the invention provides a synthesis method of a novel organic-inorganic hybrid borane compound, namely ethylenediamine-diethylborane, which is simple to operate, safe and efficient and lays a foundation for further performance research.
Drawings
FIG. 1 shows the synthesis of the borane compound ethylenediamine diethylborane in deuterated toluene of example 1 of the present invention 11 B and 11 B{ 1 h, liquid nuclear magnetic diagram, wherein the obtained target product is pure B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 。
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
In a nitrogen glove box, 0.43 g of ethylenediamine borane BH was weighed 3 NH 2 CH 2 CH 2 NH 2 BH 3 The resulting mixture was charged into a 100 mL schlenk reaction flask, the flask was sealed with a stopper, the flask was removed from the glove box, and 10 mL of 1mol/L tetrahydrofuran borane complex THF/BH was added 3 Stirring the tetrahydrofuran solution at 65 ℃ for reaction, stirring for 12 hours to finish the reaction, filtering a small amount of precipitate, and keeping the filtrate. The tetrahydrofuran solution in the filtrate is removed by rotary evaporation to obtain a viscous product, namely the target product borane compound ethylenediamine-diethylborane B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 . Calculating the resulting B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 The yield of (A) is 52%, and the purity of the product is close to 100% by nuclear magnetic detection.
Example 2
In a nitrogen glove box, 0.43 g of ethylenediamine borane BH was weighed 3 NH 2 CH 2 CH 2 NH 2 BH 3 The resulting mixture was charged into a 100 mL schlenk flask, sealed with a stopper, and the schlenk flask was removed from the glove box, followed by addition of 15 mL of 1mol/L tetrahydrofuran borane complex THF BH 3 Stirring the tetrahydrofuran solution at 40 ℃ for reaction, stirring for 28 hours to finish the reaction, filtering a small amount of precipitate, and keeping the filtrate. The tetrahydrofuran solution in the filtrate is removed by rotary evaporation to obtain a viscous product, namely the target product borane compound ethylenediamine-diethylborane B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 . Calculating the resulting B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 The yield of (A) was 61%, and the purity thereof was close to 100% by nuclear magnetic assay.
Example 3
In a nitrogen glove box, 0.43 g of ethylenediamine borane BH was weighed 3 NH 2 CH 2 CH 2 NH 2 BH 3 The resulting mixture was charged into a 100 mL schlenk reaction flask, the flask was sealed with a stopper, the flask was removed from the glove box, and 20 mL of 1mol/L tetrahydrofuran borane complex THF/BH was added 3 Stirring the tetrahydrofuran solution at 50 ℃ for reaction, stirring for 24 hours to finish the reaction, filtering a small amount of precipitate, and keeping the filtrate. The tetrahydrofuran solution in the filtrate is removed by rotary evaporation to obtain a viscous product, namely the target product ethylenediamine-diethylborane B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 . Calculating the resulting B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 The yield of (A) is 82%, and the purity of the product is close to 100% by nuclear magnetic detection.
Example 4
In a nitrogen glove box, 0.43 g of ethylenediamine borane BH was weighed 3 NH 2 CH 2 CH 2 NH 2 BH 3 The resulting mixture was charged into a 100 mL schlenk reaction flask, the flask was sealed with a stopper, the flask was removed from the glove box, and 30 mL of a 1mol/L tetrahydrofuran borane complex THF/BH was added 3 Stirring the tetrahydrofuran solution at 25 ℃ for reaction, stirring for 36 hours to finish the reaction, filtering a small amount of precipitate,the filtrate was retained. The tetrahydrofuran solution in the filtrate is removed by rotary evaporation to obtain a viscous product, namely the target product ethylenediamine-diethylborane B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 . Calculating the resulting B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 The yield of (A) is 43%, 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.
Claims (4)
1. A method for synthesizing a borane compound, namely ethylenediamine-diethylborane, is characterized by comprising the following specific steps: under the condition of no water and no oxygen, ethylenediamine borane BH is added 3 NH 2 CH 2 CH 2 NH 2 BH 3 Adding into a reaction vessel, and adding tetrahydrofuran borane complex THF-BH 3 Stirring the tetrahydrofuran solution at 25-65 ℃ to react to obtain a target product borane compound ethylenediamine-diethylborane B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 。
2. The method for synthesizing the borane compound ethylenediamine-diethylborane as in claim 1, comprising the following specific steps: in a nitrogen glove box, ethylenediamine borane BH 3 NH 2 CH 2 CH 2 NH 2 BH 3 Placing into a schlenk reaction flask, sealing with a stopper, removing the schlenk reaction flask from the glove box, and adding 1mol/L tetrahydrofuran borane complex THF. BH 3 In a solution of tetrahydrofuran of (4), wherein BH 3 NH 2 CH 2 CH 2 NH 2 BH 3 And THF. BH 3 The feeding molar ratio of (1: 2) - (1: 6) and stirring the mixture to react at the temperature of between 25 and 65 ℃ for 12 to 36h, filtering out precipitate after the reaction is finished, reserving filtrate, and performing rotary evaporation to remove tetrahydrofuran solution in the filtrate to obtain a viscous product, namely a target product borane compound ethylenediamine-diethylborane B with the purity close to 100 percent 2 H 5 NHCH 2 CH 2 NHB 2 H 5 。
3. The method of synthesizing a borane compound, ethylenediamine diborane, according to claim 1, wherein: the stirring reaction temperature in the synthesis process is 50 ℃, and BH is 3 NH 2 CH 2 CH 2 NH 2 BH 3 And THF. BH 3 The feeding molar ratio of (1) to (4) and the stirring reaction time of 24 hours.
4. The method for synthesizing the borane compound ethylenediamine diethylborane as claimed in claim 1, wherein the reaction equation in the synthesis process is as follows:
BH 3 NH 2 CH 2 CH 2 NH 2 BH 3 + 2 THF·BH 3 = B 2 H 5 NHCH 2 CH 2 NHB 2 H 5 + 2 H 2 + 2 THF。
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6048985A (en) * | 1998-12-22 | 2000-04-11 | Mine Safety Appliances Company | Borane-tetrahydrofuran complex method of storing and reacting borane-tetrahydrofuran complex |
| CN101479280A (en) * | 2006-06-26 | 2009-07-08 | 巴斯夫欧洲公司 | Borane ether complexes |
| US20130225863A1 (en) * | 2010-07-09 | 2013-08-29 | Purdue Research Foundation | Procedures for the Synthesis of Ethylenediamine Bisborane and Ammonia Borane |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6048985A (en) * | 1998-12-22 | 2000-04-11 | Mine Safety Appliances Company | Borane-tetrahydrofuran complex method of storing and reacting borane-tetrahydrofuran complex |
| CN101479280A (en) * | 2006-06-26 | 2009-07-08 | 巴斯夫欧洲公司 | Borane ether complexes |
| US20130225863A1 (en) * | 2010-07-09 | 2013-08-29 | Purdue Research Foundation | Procedures for the Synthesis of Ethylenediamine Bisborane and Ammonia Borane |
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