CN114685548A - 一种负二价硼烷阴离子钾盐的合成方法 - Google Patents
一种负二价硼烷阴离子钾盐的合成方法 Download PDFInfo
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- CBWJKNQKWLEEPG-UHFFFAOYSA-N dihydridoborate(1-) Chemical compound [BH2-] CBWJKNQKWLEEPG-UHFFFAOYSA-N 0.000 title claims abstract description 24
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 title claims abstract description 24
- 238000001308 synthesis method Methods 0.000 title claims abstract description 9
- 229910000085 borane Inorganic materials 0.000 claims abstract description 49
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 38
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910000105 potassium hydride Inorganic materials 0.000 claims abstract description 3
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 12
- 239000002244 precipitate Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 6
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- -1 ethanediamine diethylborane Chemical compound 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 7
- 238000001514 detection method Methods 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 229910003203 NH3BH3 Inorganic materials 0.000 description 1
- 229910020889 NaBH3 Inorganic materials 0.000 description 1
- 150000007960 acetonitrile Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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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 Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
本发明公开了一种负二价硼烷阴离子钾盐的合成方法,具体过程为:在无水无氧的条件下,将乙二氨二乙硼烷B2H5NHCH2CH2NHB2H5加入到氢化钾KH的四氢呋喃的悬浮液中,于−25~35℃搅拌反应制得目标产物负二价硼烷阴离子钾盐K2[(BH3)2NHCH2CH2NH(BH3)2]。本发明提供了一种新型离子型有机‑无机杂化的负二价硼烷阴离子钾盐K2[(BH3)2NHCH2CH2NH(BH3)2]的合成方法,该合成方法操作简单,安全高效,为其进一步的性能研究打下了基础。
Description
技术领域
本发明属于硼烷化合物的合成技术领域,具体涉及一种负二价硼烷阴离子钾盐的合成方法。
背景技术
硼烷是一类具有BH3结构单元或具有B-H键的含硼化合物,被广泛应用于储能材料、有机合成和催化等领域。硼烷类化合物的研究已有近百年的历史,在此期间,合成了大量的硼烷类化合物。而由于B原子的缺电子性,使得合成的硼烷化合物多数是路易斯酸碱加合类型的化合物,例如,NH3BH3,NaBH3NH2BH3,(CH3)SBH3等硼烷化合物。能够提供孤对电子与B进行配位的含N, O, P, S等原子的化合物是合成硼烷类化合物的首选配体。在这些化合物中间,含N的硼烷类化合物研究的最多,目前已经合成的有B/N链状化合物(NH3BH3,NH3BH2NH2BH3, NH3BH2NH2BH2NH2BH3, NH2B2H5)及它们带取代基的类似物、离子型的B/N链状化合物(NaNH2BH3, Na[BH3NH2BH3], Na[BH3NH2BH2NH2BH3], Na[BH(NH2BH3)3])等。含O和P的硼烷化合物也有一部分被研究,例如,C4H8OBH3, H3PBH3,频哪醇硼烷等,主要是应用于有机化学合成领域。
除上述几种B/N离子型硼烷化合物以外,还有一类有机-无机杂化的离子型硼烷类化合物,该类硼烷化合物目前研究的较少。鉴于硼烷类化合物的广泛用途,有必要设计一种有机-无机杂化的新型离子型硼烷化合物,并且设计的合成方法相对简单高效,为其应用研究打下一定的基础,进一步充实硼化学的研究。
发明内容
本发明解决的技术问题是提供了一种操作简单、安全可靠且产率较高的一种负二价硼烷阴离子钾盐的合成方法。
本发明为解决上述技术问题采用如下技术方案,一种负二价硼烷阴离子钾盐的合成方法,其特征在于具体过程为:在无水无氧的条件下,将乙二氨二乙硼烷B2H5NHCH2CH2NHB2H5加入到氢化钾KH的四氢呋喃的悬浮液中,于−25~35℃搅拌反应制得目标产物负二价硼烷阴离子钾盐K2[(BH3)2NHCH2CH2NH(BH3)2]。
进一步优选,所述的负二价硼烷阴离子钾盐K2[(BH3)2NHCH2CH2NH(BH3)2]的合成方法的具体步骤为:在氮气手套箱中,将B2H5NHCH2CH2NHB2H5和KH分别装入两个schlenk反应瓶中,用塞子密封后将schlenk反应瓶移出手套箱,再分别加入四氢呋喃作为溶剂,随后将B2H5NHCH2CH2NHB2H5的四氢呋喃溶液加入到KH的四氢呋喃的悬浮液中,其中B2H5NHCH2CH2NHB2H5和KH的投料摩尔比为1:2~1:6,于−25~35℃搅拌反应2~8 h后反应结束,过滤掉溶液,保留沉淀,真空下干燥该沉淀即得到纯度接近100%的白色粉末状的目标产物负二价硼烷阴离子钾盐K[(BH3)2NHCH2CH2NH(BH3)2]。
进一步优选,合成过程中的反应温度为20℃,B2H5NHCH2CH2NHB2H5和KH的投料摩尔比优选1:3,搅拌反应时间为4 h。
本发明所述的负二价硼烷阴离子钾盐K2[(BH3)2NHCH2CH2NH(BH3)2]的合成方法中的反应方程式为:
B2H5NHCH2CH2NHB2H5 + 2 KH = K2[(BH3)2NHCH2CH2NH(BH3)2]。
本发明与现有技术相比具有以下有益效果:本发明提供了一种新型离子型有机-无机杂化的负二价硼烷阴离子钾盐K2[(BH3)2NHCH2CH2NH(BH3)2]的合成方法,该合成方法操作简单,安全高效,为其进一步的性能研究打下了基础。
附图说明
图1是实施例1合成的负二价硼烷阴离子钾盐K2[(BH3)2NHCH2CH2NH(BH3)2]在氘代乙腈中的11B和11B{1H}液体核磁图,由图可知制得的目标产物为纯净的K2[(BH3)2NHCH2CH2NH(BH3)2]。
具体实施方式
以下通过实施例对本发明的上述内容做进一步详细说明,但不应该将此理解为本发明上述主题的范围仅限于以下的实施例,凡基于本发明上述内容实现的技术均属于本发明的范围。
实施例1
在氮气手套箱中,称取0.56 g B2H5NHCH2CH2NHB2H5和0.40 g KH分别装入两个50mL的schlenk反应瓶中,用塞子密封后将schlenk反应瓶移出手套箱,再分别加入10 mL四氢呋喃作为溶剂;随后将B2H5NHCH2CH2NHB2H5的四氢呋喃溶液加入到KH的四氢呋喃的悬浮液中,于−25℃搅拌反应8 h;此后过滤掉溶液,保留沉淀,真空下干燥该沉淀即得到白色粉末状的目标产物负二价硼烷阴离子钾盐K[(BH3)2NHCH2CH2NH(BH3)2]。计算所得到的K[(BH3)2NHCH2CH2NH(BH3)2]的产率为73%,核磁检测其纯度接近100%。
实施例2
在氮气手套箱中,称取0.56 g B2H5NHCH2CH2NHB2H5和0.40 g KH分别装入两个50mL的schlenk反应瓶中,用塞子密封后将schlenk反应瓶移出手套箱,再分别加入10 mL四氢呋喃作为溶剂;随后将B2H5NHCH2CH2NHB2H5的四氢呋喃溶液加入到KH的四氢呋喃的悬浮液中,于0℃搅拌反应6 h;此后过滤掉溶液,保留沉淀,真空下干燥该沉淀即得到白色粉末状的目标产物负二价硼烷阴离子钾盐K[(BH3)2NHCH2CH2NH(BH3)2]。计算所得到的K[(BH3)2NHCH2CH2NH(BH3)2]的产率为78%,核磁检测其纯度接近100%。
实施例3
在氮气手套箱中,称取0.56 g B2H5NHCH2CH2NHB2H5和0.60 g KH分别装入两个50mL的schlenk反应瓶中,用塞子密封后将schlenk反应瓶移出手套箱,再分别加入10 mL四氢呋喃作为溶剂;随后将B2H5NHCH2CH2NHB2H5的四氢呋喃溶液加入到KH的四氢呋喃的悬浮液中,于20℃搅拌反应4 h;此后过滤掉溶液,保留沉淀,真空下干燥该沉淀即得到白色粉末状的目标产物负二价硼烷阴离子钾盐K[(BH3)2NHCH2CH2NH(BH3)2]。计算所得到的K[(BH3)2NHCH2CH2NH(BH3)2]的产率为89%,核磁检测其纯度接近100%。
实施例4
在氮气手套箱中,称取0.56 g B2H5NHCH2CH2NHB2H5和0.80 g KH分别装入两个50mL的schlenk反应瓶中,用塞子密封后将schlenk反应瓶移出手套箱,再分别加入10 mL四氢呋喃作为溶剂;随后将B2H5NHCH2CH2NHB2H5的四氢呋喃溶液加入到KH的四氢呋喃的悬浮液中,于35℃搅拌反应2 h;此后过滤掉溶液,保留沉淀,真空下干燥该沉淀即得到白色粉末状的最终产物负二价硼烷阴离子钾盐K[(BH3)2NHCH2CH2NH(BH3)2]。计算所得到的K[(BH3)2NHCH2CH2NH(BH3)2]的产率为73%,核磁检测其纯度接近100%。
以上实施例描述了本发明的基本原理、主要特征及优点,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明原理的范围下,本发明还会有各种变化和改进,这些变化和改进均落入本发明保护的范围内。
Claims (4)
1.一种负二价硼烷阴离子钾盐的合成方法,其特征在于具体过程为:在无水无氧的条件下,将乙二氨二乙硼烷B2H5NHCH2CH2NHB2H5加入到氢化钾KH的四氢呋喃的悬浮液中,于−25~35℃搅拌反应制得目标产物负二价硼烷阴离子钾盐K2[(BH3)2NHCH2CH2NH(BH3)2]。
2.根据权利要求1所述的负二价硼烷阴离子钾盐的合成方法,其特征在于具体步骤为:在氮气手套箱中,将B2H5NHCH2CH2NHB2H5和KH分别装入两个schlenk反应瓶中,用塞子密封后将schlenk反应瓶移出手套箱,再分别加入四氢呋喃作为溶剂,随后将B2H5NHCH2CH2NHB2H5的四氢呋喃溶液加入到KH的四氢呋喃的悬浮液中,其中B2H5NHCH2CH2NHB2H5和KH的投料摩尔比为1:2~1:6,于−25~35℃搅拌反应2~8 h后反应结束,过滤掉溶液,保留沉淀,真空下干燥该沉淀即得到纯度接近100%的白色粉末状的目标产物负二价硼烷阴离子钾盐K[(BH3)2NHCH2CH2NH(BH3)2]。
3.根据权利要求1或2所述的负二价硼烷阴离子钾盐的合成方法,其特征在于:合成过程中的反应温度为20℃,B2H5NHCH2CH2NHB2H5和KH的投料摩尔比优选1:3,搅拌反应时间为4h。
4.根据权利要求1或2所述的负二价硼烷阴离子钾盐的合成方法,其特征在于合成过程中的反应方程式为:
B2H5NHCH2CH2NHB2H5 + 2 KH = K2[(BH3)2NHCH2CH2NH(BH3)2]。
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US6048985A (en) * | 1998-12-22 | 2000-04-11 | Mine Safety Appliances Company | Borane-tetrahydrofuran complex method of storing and reacting borane-tetrahydrofuran complex |
CN101479280A (zh) * | 2006-06-26 | 2009-07-08 | 巴斯夫欧洲公司 | 硼烷醚络合物 |
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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Publication number | Priority date | Publication date | Assignee | Title |
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US6048985A (en) * | 1998-12-22 | 2000-04-11 | Mine Safety Appliances Company | Borane-tetrahydrofuran complex method of storing and reacting borane-tetrahydrofuran complex |
CN101479280A (zh) * | 2006-06-26 | 2009-07-08 | 巴斯夫欧洲公司 | 硼烷醚络合物 |
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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