CN108676023A - 一种高效制备硼氢阴离子[RnH4-nB]-的方法 - Google Patents
一种高效制备硼氢阴离子[RnH4-nB]-的方法 Download PDFInfo
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- CN108676023A CN108676023A CN201810493658.9A CN201810493658A CN108676023A CN 108676023 A CN108676023 A CN 108676023A CN 201810493658 A CN201810493658 A CN 201810493658A CN 108676023 A CN108676023 A CN 108676023A
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- hydride ion
- boron hydride
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- 229910010277 boron hydride Inorganic materials 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 28
- -1 boron hydride ion Chemical class 0.000 claims abstract description 60
- 239000001257 hydrogen Substances 0.000 claims abstract description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 20
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 15
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 7
- 229910000077 silane Inorganic materials 0.000 claims abstract description 7
- 239000002841 Lewis acid Substances 0.000 claims abstract description 5
- 150000007517 lewis acids Chemical class 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 13
- 239000000010 aprotic solvent Substances 0.000 claims description 8
- 229910052796 boron Inorganic materials 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910000085 borane Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 238000003760 magnetic stirring Methods 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 150000001768 cations Chemical class 0.000 claims description 4
- 239000011968 lewis acid catalyst Substances 0.000 claims description 4
- PARWUHTVGZSQPD-UHFFFAOYSA-N phenylsilane Chemical compound [SiH3]C1=CC=CC=C1 PARWUHTVGZSQPD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- DBDNZCBRIPTLJF-UHFFFAOYSA-N boron(1-) monohydride Chemical class [BH-] DBDNZCBRIPTLJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 125000002091 cationic group Chemical group 0.000 claims description 2
- VDCSGNNYCFPWFK-UHFFFAOYSA-N diphenylsilane Chemical compound C=1C=CC=CC=1[SiH2]C1=CC=CC=C1 VDCSGNNYCFPWFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005052 trichlorosilane Substances 0.000 claims description 2
- 125000003963 dichloro group Chemical group Cl* 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 12
- MXSVLWZRHLXFKH-UHFFFAOYSA-N triphenylborane Chemical compound C1=CC=CC=C1B(C=1C=CC=CC=1)C1=CC=CC=C1 MXSVLWZRHLXFKH-UHFFFAOYSA-N 0.000 abstract description 10
- 239000003054 catalyst Substances 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 4
- 238000010189 synthetic method Methods 0.000 abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000001638 boron Chemical class 0.000 description 6
- 238000006197 hydroboration reaction Methods 0.000 description 6
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 5
- UCRIXEWTILHNCG-UHFFFAOYSA-N 1-ethyl-2h-pyridine Chemical compound CCN1CC=CC=C1 UCRIXEWTILHNCG-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 4
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Substances BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical class CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- UCXUKTLCVSGCNR-UHFFFAOYSA-N diethylsilane Chemical compound CC[SiH2]CC UCXUKTLCVSGCNR-UHFFFAOYSA-N 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 229910000033 sodium borohydride Inorganic materials 0.000 description 2
- 239000012279 sodium borohydride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LALRXNPLTWZJIJ-UHFFFAOYSA-N triethylborane Chemical group CCB(CC)CC LALRXNPLTWZJIJ-UHFFFAOYSA-N 0.000 description 2
- AMFMJCAPWCXUEI-UHFFFAOYSA-M 1-ethylpyridin-1-ium;chloride Chemical compound [Cl-].CC[N+]1=CC=CC=C1 AMFMJCAPWCXUEI-UHFFFAOYSA-M 0.000 description 1
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 1
- 125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 229910015845 BBr3 Inorganic materials 0.000 description 1
- 229910015844 BCl3 Inorganic materials 0.000 description 1
- 239000004604 Blowing Agent Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000012448 Lithium borohydride Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- BCAARMUWIRURQS-UHFFFAOYSA-N dicalcium;oxocalcium;silicate Chemical compound [Ca+2].[Ca+2].[Ca]=O.[O-][Si]([O-])([O-])[O-] BCAARMUWIRURQS-UHFFFAOYSA-N 0.000 description 1
- 125000004188 dichlorophenyl group Chemical group 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000003335 steric effect Effects 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F5/027—Organoboranes and organoborohydrides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/061—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/063—Tetrafluoboric acid; Salts thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/18—Salts thereof
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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Abstract
本发明公开了一种高效制备硼氢阴离子[RnH4‑nB]‑的方法，以路易斯酸RnX3‑nB为催化剂，氢硅烷为还原剂，可将各类卤代硼阴离子铵盐[R`4N]+[RnX4‑nB]‑还原为对应的硼氢阴离子铵盐[R`4N]+[RnH4‑nB]‑。该方法不但可制备BH4 ‑阴离子盐、三苯基硼氢化铵盐[Ph3HB]‑，而且还可合成各种其它类型的[RnH4‑nB]‑硼氢阴离子，适用性广，合成方法简单、高效。本发明为[RnH4‑nB]‑硼氢阴离子的合成提供新途径。
Description
技术领域
本发明涉及硼氢阴离子合成技术领域，具体涉及一种高效制备硼氢阴离子[RnH4-nB]-的方法。
背景技术
硼氢化钠、硼氢化钾、硼氢化锂等硼氢化盐是最为常见的无机碱金属硼氢化盐，其被广泛应用于醛酮及羧酸衍生物还原、塑料发泡剂、污水的处理剂、造纸漂白剂、储氢材料等领域。文献中报道的关于碱金属硼氢化盐的研究很多，但关于含烷基的硼氢化盐的相关研究报道较少。在硼氢化盐的阴离子或阳离子中引入烷基可以改变化合物极性、增强溶解性能从而提高其还原能力和反应活性，烷基的引入还可改变硼氢化盐的位阻效应，从而使其具有更好的立体和区域选择性。目前文献中还没有一种可以有效合成各类烷基硼氢化盐的方法，这也限制了对烷基硼氢化盐性能的研究及应用。
文献DOI:10.1002/anie.201309044报道了一种1,3-二烷基咪唑氯盐与硼氢化钠在液氨中反应高效制备BH4 -烷基咪唑盐的方法，该方法不但可以得到液态的BH4 -盐类离子液体，而且产率接近100％，但该方法反应要在易燃易挥发强刺激性的液氨中进行，且不能制备烷基硼氢或卤代硼氢的阴离子盐，只能合成BH4 -阴离子盐。
专利CN200310111451.4报道了一种使用季胺化的壳聚糖树脂与硼氢化钾在碱性水溶液中进行离子交换制备壳聚糖支载含BH4 -阴离子的高分子树脂的方法。该树脂可装柱用于含羰基化合物和寡糖的还原领域，但该方法同样不能制备烷基硼氢或卤代硼氢的阴离子盐，只能合成含BH4 -阴离子的高分子树脂。
专利CN 201410415290.6报道了一种三芳基硼氢化铵盐的制备方法，卤代铵盐、氢硅烷、三芳基硼烷在氯仿中反应可以高效的得到三芳基硼氢化铵盐，该三芳基硼氢化铵盐可用于有机合成中的催化加氢反应。该方法仅适用于三芳基硼烷，且只能合成单氢取代硼氢化铵盐。
上述的合成硼氢阴离子盐的方法可总结为离子交换法和氢化还原法。离子交换法仅能合成BH4 -阴离子盐，而氢化还原法也只能得到单氢的三苯基硼氢化铵盐[Ph3HB]-，以上合成方法产物单一，适用性较差，均不能用于合成其它类型的[RnH4-nB]-硼氢阴离子。
发明内容
为解决上述问题，本发明提供了一种高效制备硼氢阴离子[RnH4-nB]-的方法，以路易斯酸RnX3-nB为催化剂，氢硅烷为还原剂，可将各类卤代硼阴离子铵盐 [R`4N]+[RnX4-nB]-还原为对应的硼氢阴离子铵盐[R`4N]+[RnH4-nB]-。该方法不但可制备BH4 -阴离子盐、三苯基硼氢化铵盐[Ph3HB]-，而且还可合成各种其它类型的[RnH4-nB]-硼氢阴离子，适用性广，合成方法简单、高效。本发明为[RnH4-nB]-硼氢阴离子的合成提供新途径。
为实现上述目的，本发明采取的技术方案为：
一种高效制备硼氢阴离子[RnH4-nB]-的方法，包括如下步骤：
S1、反应在惰性气体保护下进行，首先向反应瓶中加入mxg(Xmol)的卤代硼阴离子铵盐[R`4N]+[RnX4-nB]-，再加入30-20mxg的干燥的非质子溶剂，在磁力搅拌下使[R`4N]+[RnX4-nB]-盐完全溶解；
S2、惰性气体保护下向上述反应瓶中补加0.1-0.005Xmol的路易斯酸催化剂，5-1Xmol的氢硅烷还原剂，在20-40℃下搅拌反应10-48小时， [R`4N]+[RnX4-nB]-被完全还原为硼氢阴离子盐[R`4N]+[RnH4-nB]-；
所述的硼氢阴离子盐[R`4N]+[RnH4-nB]-中的阳离子特指为铵盐阳离子以[R`4N]+表示，对应的硼氢阴离子以[RnH4-nB]-表示；n可以为0、1、2、3中的任意一数值；当n＝0时，[RnH4-nB]-为BH4 -阴离子；当n＝1、2、3时，[RnH4-nB]-为含烷基或芳基的硼氢阴离子。
优选地，所述步骤S1中惰性气体为高纯氮气或者高纯氩气；反应瓶可以为溶剂储存瓶、反应管或圆底烧瓶等玻璃仪器，优选溶剂储存瓶、反应管。
优选地，所述步骤S1中的卤代硼阴离子铵盐[R`4N]+[RnX4-nB]-中的[R`4N]+为铵盐阳离子其不参与反应，其可为常见的铵盐阳离子，如：烷基咪唑类阳离子、吡啶类阳离子、环己胺类阳离子、烷基胺类阳离子、芳胺类阳离子等； [RnX4-nB]-为卤代硼阴离子，反应中被还原为硼氢阴离子[RnH4-nB]-，X为卤素，如F、Cl、Br等；当n＝0时，[Rn X4-nB]-可以为BF4 -、BCl4 -、BBr4 -；当n＝1、2、 3时，[RnX4-nB]-可以为BPhF3 -、BPhCl3 -、BPh2F2 -、BPh2Cl2 -、BPh3F-、BPh3Cl-、BPh3Br-、BEt2F2 -、BEt2Cl2 -、BEt3Cl-、BEt3Br-等烃基卤代硼烷阴离子；[RnX4-nB]-中R为常见的芳基或烷基，如苯基、对甲基苯基、萘基、乙基、异丙基、正丁基等基团。
优选地，所述步骤S1的卤代硼阴离子铵盐[R`4N]+[RnX4-nB]-可通过卤化铵盐与硼烷反应制备：在惰性气体保护下进行，反应瓶中加入等物质量的卤化烷基铵盐[R`4N]+X-和硼烷RnX3-nB，再加入30-20mxg的干燥的非质子溶剂，在磁力搅拌下反应0.2-2小时，反应生成[R`4N]+[RnX4-nB]-盐可直接用于下一步的反应。
优选地，所述步骤S1中加入的[R`4N]+[RnX4-nB]-的质量以mx表示，对应的物质的量为Xmol，X的范围优选0.0001-1moL。
优选地，所述步骤S1中干燥的非质子溶剂是指不含水的氯仿、二氯甲烷、苯、甲苯、乙醚、四氢呋喃等非质子溶剂。
优选地，所述步骤S2中的路易斯酸催化剂是指常规的路易斯酸，如：AlCl3、 FeCl3、BCl3、BBr3等以及烃基硼烷及芳基硼烷等。
优选地，所述步骤S2中的氢硅烷可以是苯硅烷、二苯基硅烷、三乙基硅烷、二氯氢硅、三氯氢硅、三乙氧基硅烷中的任意一种。
本发明具有以下有益效果：
任意类型的硼氢化铵盐[R`4N]+[RnH4-nB]-都可以使用此方法合成，如制备 BH4 -阴离子盐、三苯基硼氢化铵盐[Ph3HB]-，以及各种其它类型的[RnH4-nB]-硼氢阴离子，该方法适用性较广；该方法以廉价的卤化铵盐[R`4N]+X-为原料、常见的路易斯酸为催化剂合成各类硼氢化铵盐[R`4N]+[RnH4-nB]-，不但成本较低，而且合成方法简单高效。
具体实施方式
为了使本发明的目的及优点更加清楚明白，以下结合实施例对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
实施例1
1,3-二甲基咪唑四氢化硼盐的合成
反应在氩气保护下进行，首先向带有真空旋塞的50ml的反应管中加入 0.5g(2.7mmol)的1,3-二甲基咪唑四氟硼酸盐，再加入10g的干燥的无水二氯甲烷溶剂，在磁力搅拌下使1,3-二甲基咪唑四氟硼酸盐完全溶解。完全溶解后向反应管中补加0.27mmol的三溴化硼作为催化剂，5.4mmol的苯硅烷还原剂，在35℃下搅拌反应10小时，1,3-二甲基咪唑四氟硼酸盐被完全还原为 1,3-二甲基咪唑四氢化硼盐。
实施例2
1-甲基-3-正丁基咪唑氢化三苯基硼盐的合成
反应在高纯氮气保护下进行，首先向带有真空旋塞的50ml的反应管中加入0.8g(4.6mmol)的氯化1-甲基-3-正丁基咪唑盐，再加入4.6mmol的三苯基硼烷以及24g的干燥的氯仿，在磁力搅拌下反应1小时，反应生成1-甲基-3-正丁基咪唑氯化三苯基硼盐。再向上述溶液中补加0.05mmol的三苯基硼烷作为催化剂，10mmol的二乙基硅烷还原剂，在40℃下搅拌反应24小时， 1-甲基-3-正丁基咪唑氯化三苯基硼盐被完全还原为1-甲基-3-正丁基咪唑氢化三苯基硼盐。
实施例3
1-甲基-3-正丁基咪唑三氢苯基硼盐的合成
在实施例2中将4.6mmol的三苯基硼烷替换为4.6mmol的二氯苯基硼烷，其余步骤同于实施例2，最终得到产物1-甲基-3-正丁基咪唑三氢苯基硼盐。
实施例4
N-乙基吡啶四氢化硼盐的合成
在实施例1中将0.5g(2.7mmol)的1,3-二甲基咪唑四氟硼酸盐替换为 0.5g(2.56mmol)的N-乙基吡啶四氟硼酸盐，将三溴化硼替换为三氯化铝，其余步骤同于实施例1，最终得到N-乙基吡啶四氢化硼盐。
实施例5
N-乙基吡啶氢化三乙基硼盐的合成
在实施例2中将0.8g(4.6mmol)的氯化1-甲基-3-正丁基咪唑盐替换为0.6g(4.17mmol)的氯化N-乙基吡啶盐，将4.6mmol的三苯基硼烷替换为4.6mmol的三乙基硼烷，0.05mmol的三苯基硼烷替换为0.08mmol的三乙基硼烷，10mmol的二乙基硅烷还原剂替换为8mmol的苯硅烷，最后得到N-乙基吡啶氢化三乙基硼盐。
以上所述仅是本发明的优选实施方式，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以作出若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。
Claims (8)
1.一种高效制备硼氢阴离子[RnH4-nB]-的方法，其特征在于，包括如下步骤：
S1、反应在惰性气体保护下进行，首先向反应瓶中加入mxg的卤代硼阴离子铵盐[R`4N]+[RnX4-nB]-，再加入30-20mxg的干燥的非质子溶剂，在磁力搅拌下使[R`4N]+[RnX4-nB]-盐完全溶解；
S2、惰性气体保护下向上述反应瓶中补加0.1-0.005Xmol的路易斯酸催化剂，5-1Xmol的氢硅烷还原剂，在20-40℃下搅拌反应10-48小时，[R`4N]+[RnX4-nB]-被完全还原为硼氢阴离子盐[R`4N]+[RnH4-nB]-；
所述的硼氢阴离子盐[R`4N]+[RnH4-nB]-中的阳离子特指为铵盐阳离子以[R`4N]+表示，对应的硼氢阴离子以[RnH4-nB]-表示；n可以为0、1、2、3中的任意一数值；当n＝0时，[RnH4- nB]-为BH4 -阴离子；当n＝1、2、3时，[RnH4-nB]-为含烷基或芳基的硼氢阴离子。
2.如权利要求1所述的一种高效制备硼氢阴离子[RnH4-nB]-的方法，其特征在于，所述步骤S1中惰性气体为高纯氮气或者高纯氩气；反应瓶可以为溶剂储存瓶、反应管或圆底烧瓶。
3.如权利要求1所述的一种高效制备硼氢阴离子[RnH4-nB]-的方法，其特征在于，所述步骤S1中的卤代硼阴离子铵盐[R`4N]+[RnX4-nB]-中的[R`4N]+为铵盐阳离子其不参与反应，其可为常见的铵盐阳离子；[RnX4-nB]-为卤代硼阴离子，反应中被还原为硼氢阴离子[RnH4- nB]-，X为卤素，当n＝0时，[RnX4-nB]-可以为BF4 -、BCl4 -、BBr4 -；当n＝1、2、3时，[RnX4-nB]-可以为BPhF3 -、BPhCl3 -、BPh2F2 -、BPh2Cl2 -、BPh3F-、BPh3Cl-、BPh3Br-、BEt2F2 -、BEt2Cl2 -、BEt3Cl-、BEt3Br-；[RnX4-nB]-中R为常见的芳基或烷基。
4.如权利要求1所述的一种高效制备硼氢阴离子[RnH4-nB]-的方法，其特征在于，所述步骤S1的卤代硼阴离子铵盐[R`4N]+[RnX4-nB]-可通过卤化铵盐与硼烷反应制备：在惰性气体保护下进行，反应瓶中加入等物质量的卤化烷基铵盐[R`4N]+X-和硼烷RnX3-nB，再加入30-20mxg的干燥的非质子溶剂，在磁力搅拌下反应0.2-2小时，反应生成[R`4N]+[RnX4-nB]-盐可直接用于下一步的反应。
5.如权利要求1所述的一种高效制备硼氢阴离子[RnH4-nB]-的方法，其特征在于，所述步骤S1中加入的[R`4N]+[RnX4-nB]-的质量以mx表示，对应的物质的量为Xmol，X的取值范围为0.0001-1moL。
6.如权利要求1所述的一种高效制备硼氢阴离子[RnH4-nB]-的方法，其特征在于，所述步骤S1中干燥的非质子溶剂是指不含水的非质子溶剂。
7.如权利要求1所述的一种高效制备硼氢阴离子[RnH4-nB]-的方法，其特征在于，所述步骤S2中的路易斯酸催化剂是指常规的路易斯酸。
8.如权利要求1所述的一种高效制备硼氢阴离子[RnH4-nB]-的方法，其特征在于，所述步骤S2中的氢硅烷可以是苯硅烷、二苯基硅烷、三乙基硅烷、二氯氢硅、三氯氢硅、三乙氧基硅烷中的任意一种。
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