CN105949229A - Synthetic method of B-substituted aminoborane - Google Patents
Synthetic method of B-substituted aminoborane Download PDFInfo
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- 238000010189 synthetic method Methods 0.000 title claims abstract description 12
- TVJORGWKNPGCDW-UHFFFAOYSA-N aminoboron Chemical class N[B] TVJORGWKNPGCDW-UHFFFAOYSA-N 0.000 title abstract 2
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 66
- UORVGPXVDQYIDP-UHFFFAOYSA-N trihydridoboron Substances B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 27
- 229910000085 borane Inorganic materials 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 23
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 22
- 239000000706 filtrate Substances 0.000 claims description 19
- UYVXZUTYZGILQG-UHFFFAOYSA-N methoxyboronic acid Chemical compound COB(O)O UYVXZUTYZGILQG-UHFFFAOYSA-N 0.000 claims description 19
- 229910000069 nitrogen hydride Inorganic materials 0.000 claims description 16
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 15
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 14
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000004327 boric acid Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
- 229910052744 lithium Inorganic materials 0.000 claims description 9
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 6
- MMCPOSDMTGQNKG-UHFFFAOYSA-N anilinium chloride Chemical compound Cl.NC1=CC=CC=C1 MMCPOSDMTGQNKG-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- CPDRCKWKDRDHPW-UHFFFAOYSA-N boric acid;naphthalene Chemical compound OB(O)O.C1=CC=CC2=CC=CC=C21 CPDRCKWKDRDHPW-UHFFFAOYSA-N 0.000 claims 1
- 239000004210 ether based solvent Substances 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 25
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000003638 chemical reducing agent Substances 0.000 abstract description 4
- -1 lithium aluminum hydride Chemical compound 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000011232 storage material Substances 0.000 abstract description 4
- PLFLRQISROSEIJ-UHFFFAOYSA-N methylborane Chemical compound CB PLFLRQISROSEIJ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000011160 research Methods 0.000 abstract description 2
- KKAXNAVSOBXHTE-UHFFFAOYSA-N boranamine Chemical class NB KKAXNAVSOBXHTE-UHFFFAOYSA-N 0.000 abstract 3
- 238000009776 industrial production Methods 0.000 abstract 1
- 239000003960 organic solvent Substances 0.000 abstract 1
- 239000012429 reaction media Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 51
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 40
- 229910010084 LiAlH4 Inorganic materials 0.000 description 26
- 239000007787 solid Substances 0.000 description 23
- 238000001556 precipitation Methods 0.000 description 14
- 229910010082 LiAlH Inorganic materials 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 8
- 235000004237 Crocus Nutrition 0.000 description 6
- 241000596148 Crocus Species 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000001897 boron-11 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 229910003203 NH3BH3 Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 238000004607 11B NMR spectroscopy Methods 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- LEMABCWCFKCYQC-UHFFFAOYSA-N OBO.C1=CC=CC2=CC=CC=C21 Chemical class OBO.C1=CC=CC2=CC=CC=C21 LEMABCWCFKCYQC-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical class [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- LGZXYFMMLRYXLK-UHFFFAOYSA-N mercury(2+);sulfide Chemical group [S-2].[Hg+2] LGZXYFMMLRYXLK-UHFFFAOYSA-N 0.000 description 1
- NQMRYBIKMRVZLB-UHFFFAOYSA-N methylamine hydrochloride Chemical compound [Cl-].[NH3+]C NQMRYBIKMRVZLB-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000013638 trimer Substances 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to a synthetic method of a B-substituted group aminoborane derivative. The synthetic method adopts the specific process as follows: with methyl boron, lithium aluminum hydride and ammonium salt as raw materials, and an organic solvent as a reaction medium, the B-methyl substituted aminoborane derivative is synthesized through ordinary chemical reaction. The B-substituted aminoborane can be used as a hydrogen storage material and as a reducing agent. The invention provides a novel synthetic method of the aminoborane derivative, so that great convenience is provided for future scientific research and industrial production. The synthetic method provided by the invention is simple, low in cost and mild in reaction temperature; reaction can take place at the room temperature; and the obtained product is relatively high in purity.
Description
Technical field
The present invention relates to the synthetic method of a kind of B substituted-amino borine, belong to hydrogen storage material field.
Background technology
Along with the development of demographic and economic, people are increasing to the demand of high efficient energy sources.Hydrogen is novel clearly as one
The clean energy, has enthalpy of combustion high, light weight, and source is wide, and combustion product is the advantage of water.Hydrogen storage is the key issue utilizing Hydrogen Energy
One of, boron hydride complex has higher theoretical hydrogen content, NaBH4Hydrogen content be 10.6wt%, NH3BH3Then reach
19.5wt%, can react generation hydrogen with water in alkalescence or neutral medium under the effect of catalyst, but apply in reality
In still suffer from problems, such as noble metal (Pt, Ru etc.) used, catalyst cost is high, catalytic efficiency is low, service life is short
Etc. problem.NH3BH3Thermal decomposition can also discharge hydrogen, but decomposition temperature is high, there is side reaction, impure in hydrogen.At ammonia
Introducing substituted radical on borine and perhaps can solve these problems, ammonia borane derivative in the market mainly adds on N
Enter substituent group, increase molecular volume, seldom have B substituted radical ammonia borine.
B substituent methyl ammonia borine can discharge 2 molecule hydrogen at 150 DEG C or when there is catalyst 80 DEG C, generates ring-type
Trimer, product can be regenerated as raw material under certain condition.
B substituted radical ammonia borine is except can serve as hydrogen storage material, it is also possible to making reducing agent, its reproducibility is weaker than ammonia boron
Alkane, may be used for regulating and controlling the size of nanoparticle.
Summary of the invention
The technical problem to be solved is the synthetic method providing a kind of B to replace ammonia borine.
The concrete technical scheme of the present invention is as follows:
Organic boronic and lithium aluminium hydride reduction, and difference is weighed respectively according to mol ratio organic boronic/lithium aluminium hydride reduction=1:1-1:2
Being dissolved in appropriate absolute ether, after hybrid reaction, filter, collect filtrate, evacuation removes ether solvent, obtains product organic
Borine lithium；
Being dissolved in absolute ether by organo-borane lithium, add ammonium salt reaction 1-3h, filter, collect filtrate, evacuation removes
Remove ether solvent, obtain product B substituted radical ammonia borine.
Described organic boronic is alkyl borane lithium or aromatic radical borine lithium.
Described boric acid is the boronic acid derivatives such as methyl-boric acid, phenylboric acid, naphthalene boronic acids, and ammonium salt is NH4Cl、(NH4)2SO4、
CH3NH3The ammonium salt such as Cl, anilinechloride.
The method of the present invention is with absolute ether as solvent, is organic boron with strong reductant lithium aluminium hydride reduction organic boronic
Alkane lithium, then react with ammonium salt, by common chemical reactive synthesis B substituted radical ammonia borine.This reaction can occur in room temperature,
Generate a large amount of H2, reaction must be in the environment of anhydrous and oxygen-free, and therefore, solvent must first remove water, reacts the hands at full argon
Casing is carried out.In preparation process, other product of generation such as aikyiaiurnirsoxan beta, lithium chloride all do not dissolve in solvent, can pass through
Filter, be evaporated solvent, it is possible to obtain product.The B substituted radical ammonia borine productivity of this method synthesis is high, purity
High.
The synthesis path of the present invention is as follows:
LiAlH4+B(OH)2-R→Li+BH3 --R
Li+BH3 --R+NH3-R’→R-BH2NH2-R ' (R=CH3,C6H5or C10H7R '=H, CH3,C6H5)
Beneficial effects of the present invention is presented as:
Not having B-substituted radical ammonia borine to sell in the market, we have simple method to synthesize this ammonia borine to spread out
Biology, it both can make reducing agent, it is also possible to makees hydrogen storage material, and it is the most convenient to provide for later scientific research.
Accompanying drawing explanation
Fig. 1 is B (OH)2CH3's1H NMR spectra；
Fig. 2 is B (OH)2CH3's11B NMR spectra；
Fig. 3 is NH3BH2CH3's1H NMR spectra；
Fig. 4 is NH3BH2CH3's11B NMR spectra；
Fig. 5 is CH3NH2BH2CH3's1H NMR spectra；
Fig. 6 is CH3NH2BH2CH3's13C NMR spectra.
Detailed description of the invention
In order to be more fully understood that present disclosure, below in conjunction with specific embodiment, present disclosure is done further
Illustrate, but the protection content of the present invention is not limited to following example.
Embodiment 1
A certain amount of LiAlH is weighed respectively in glove box4Being dissolved in appropriate absolute ether with methyl-boric acid, stirring makes it
Dissolve, to LiAlH4Adding a small amount of 2,2 bipyridyls in solution and make indicator, white solution becomes crocus.By methyl-boric acid
Solution is slowly added drop-wise to LiAlH4In solution, produce a large amount of hydrogen and solid precipitation, work as LiAlH4When solution becomes colorless,
LiAlH4Just reacted, but crocus solid precipitation can disturb realization, caused being difficult to judge terminal.Therefore, LiAlH is changed4
With the ratio of methyl-boric acid, do some row experiments, judge reactant optimum charging ratio according to the nuclear magnetic resonance map of end product
Example.Work as LiAlH4After methyl-boric acid reaction completely, use syringe-driven filter filtering solution, filtrate is drained with vacuum pump,
To intermediate product LiBH3CH3.By LiBH3CH3It is dissolved in absolute ether, the appropriate ammonium chloride (LiBH such as is added thereto to3CH3
It is set to 2:1,1:1,1:2 with the molar ratio of ammonium chloride), reaction occurs at once, releases a large amount of gas, at room temperature reacts
1-3h.Use syringe-driven filter filtering solution, discard solid impurity, absolute ether vacuum pump is taken out major part, wherein
Add anhydrous pentane, the raw a large amount of white solids precipitation of analysis immediately, wash solid 2-3 time with anhydrous pentane, product is carried out
Analyze, determine optimal LiBH3CH3/ ammonium chloride ratio.Experiment finds LiBH3CH3When/ammonium chloride is 1:1, react the completeest
Entirely.Nuclear magnetic spectrogram determines that this white solid is product NH3BH2CH3, productivity reaches more than 80%.Fig. 1 and Fig. 2 is raw material first respectively
Ylboronic acid1H NMR spectra and11B NMR spectra, Fig. 3 and Fig. 4 is product NH respectively3BH2CH3's1H NMR spectra and11B NMR
Collection of illustrative plates, as can be seen from the figure raw material has been substantially transitioned to product, and purity is higher.
Embodiment 2
Experiment can be simplified by embodiment 1.Weigh optimal proportion (lithium aluminium hydride reduction and methyl-boric acid mol ratio are 5:3) respectively
LiAlH4It is dissolved in appropriate absolute ether with methyl-boric acid, methyl-boric acid solution is slowly added drop-wise to LiAlH4In solution, produce
A large amount of hydrogen and solid precipitation, reacted rear filtering solution.The chlorine with raw material methyl-boric acid equimolar amounts is added in filtrate
Change ammonium, filter after reaction certain time.Evacuation removes major part solvent, adds a large amount of anhydrous pentane, separates out white solid
Product NH3BH2CH3。
Embodiment 3
With LiBH in example 23CH3It is raw material with ammonium chloride, thus it is possible to vary raw material, uses LiBH3CH3React with ammonium sulfate
Preparation NH3BH2CH3.The LiAlH of optimal proportion is weighed respectively in glove box4It is dissolved in appropriate absolute ether with methyl-boric acid,
Just methyl-boric acid solution is slowly added drop-wise to LiAlH4In solution, produce a large amount of hydrogen and solid precipitation, filter after having reacted
Solution.Add in filtrate and appropriate ammonium sulfate (LiBH3CH3/(NH4)2SO4Ratio be set to 1:1,2:1,4:1), instead
Clear transparent solutions should be filtrated to get after certain time.Evacuation removes major part solvent, adds a large amount of anhydrous pentane, separates out
White crystals, washing is done nmr analysis after drying, is shown as NH3BH2CH3.It is by series of parallel experiment, determines that raw material is thrown
Material mol ratio LiBH3CH3/(NH4)2SO4For best during 2:1.
Embodiment 4
Similar to Example 3, raw material sulphuric acid ammonium is become anilinechloride.LiAlH at glove box optimal proportion4And first
Ylboronic acid is dissolved in appropriate absolute ether, and just methyl-boric acid solution is slowly added drop-wise to LiAlH4In solution, produce a large amount of hydrogen
And solid precipitation, use syringe-driven filter filter mixed liquor after the reaction regular hour, discard solid impurity.Add in filtrate
With the anilinechloride of methyl-boric acid equimolar amounts, continue to be stirred at room temperature 2h, filter mixed solution.Filtrate is taken out glove
Case, removes major part absolute ether solvent with biexhaust pipe, oil pump device evacuation, makes solution be substantially saturated.In saturated solution
Add pentane, separate out solid product C6H5NH2BH2CH3。
Embodiment 5
Weigh the LiAlH of optimal proportion respectively4It is dissolved in (lithium aluminium hydride reduction and methyl boron in appropriate absolute ether with methyl-boric acid
Acid mol ratio is 5:3), just methyl-boric acid solution is slowly added drop-wise to LiAlH4In solution, produce a large amount of hydrogen and solid precipitation,
React rear filtering solution.The methylamine hydrochloride with methyl-boric acid equimolar amounts is added, after reaction certain time in filtrate
Filter.Evacuation removes major part solvent, adds a large amount of anhydrous pentane, separates out white crystals, and washing is done nuclear-magnetism after drying and divided
Analysis, is shown as CH3NH2BH2CH3.Fig. 5 and Fig. 6 CH respectively3NH2BH2CH3's1H H NMR spectroscopy and13C H NMR spectroscopy, it can be seen that product
Purity is the highest, almost without miscellaneous peak.
Embodiment 6
A certain amount of LiAlH is weighed respectively in glove box4It is dissolved in appropriate absolute ether with phenylboric acid, to LiAlH4Molten
Adding a small amount of 2,2 bipyridyls in liquid and make indicator, white solution becomes crocus.Phenylboric acid solution is added drop-wise to LiAlH4Solution
In, producing a large amount of hydrogen and solid precipitation, precipitation granule is relatively big, and solution is layered, and upper strata is crocus clear solution, and lower floor is Fructus Citri tangerinae
Yellow solid.Work as LiAlH4When solution becomes colorless, LiAlH4Just reacted, used syringe-driven filter filtering solution.To filtrate
Middle addition and the NH of phenylboric acid equimolar amounts4Cl, reaction immediately begins to, and releases a large amount of bubble, at room temperature reacts 1-3h.Use pin
Hair style filter filtering solution, takes out major part absolute ether vacuum pump, retains a small amount of solvent, be added thereto to a large amount of nothing
Water pentane, separates out product NH3BH2C6H5。
Embodiment 7
Weigh appropriate LiAlH respectively4And phenylboric acid, it is dissolved in absolute ether, to LiAlH4Solution adds a small amount of 2,2
Bipyridyl makees indicator, and white solution becomes crocus.Phenylboric acid solution is added drop-wise to LiAlH4In solution, produce a large amount of hydrogen
And solid precipitation, work as LiAlH4When solution becomes colorless, use syringe-driven filter filtering solution.Add and phenylboric acid in filtrate
The CH of equimolar amounts3NH3Cl, releases a large amount of hydrogen immediately.After at room temperature reaction a period of time, filter with syringe-driven filter
Solution, takes out major part by absolute ether vacuum pump, is added thereto to anhydrous pentane, obtains product CH3NH2BH2C6H5,
Sand core funnel washs 3-4 time with anhydrous pentane.
Embodiment 8
By 100mg LiAlH in glove box4It is dissolved in 5ml absolute ether, additionally weighs 183mg phenylboric acid and be dissolved in 8ml
In absolute ether, stirring is allowed to dissolve.Phenylboric acid solution is slowly added drop-wise to LiAlH4In solution, produce a large amount of white precipitate also
Emerge bubble.Reaction 30min is continued, with the syringe-driven filter filter mixed liquor of a diameter of 5cm after dripping.To water white transparency
Filtrate in add 100mg (NH4)2SO4, react 2h, filter, discard solid impurity.Major part is taken out molten with oil pump cold well device
Agent absolute ether, is added thereto to a large amount of anhydrous pentane, obtains product as white solid NH3BH2C6H5.Wash with anhydrous pentane
Wash product 2-3 time.
Embodiment 9
Appropriate LiAlH is weighed in glove box4With phenylboric acid (lithium aluminium hydride reduction and phenylboric acid mol ratio are 5:4), difference
It is dissolved in absolute ether.Phenylboric acid solution is slowly added drop-wise to LiAlH4In solution, it is immediately generated white solid and precipitates and emit
Go out bubble.Continuing stirring 30min after dripping makes reaction complete, is filtrated to get achromaticity and clarification clear solution.Add in filtrate
C with phenylboric acid equimolar amounts6H5NH3Cl, generates a large amount of gas at once.After reaction 2h, filter mixing with syringe-driven filter molten
Liquid, takes out major part solvent absolute ether with oil pump cold well device, is added thereto to a large amount of anhydrous pentane, obtains product
C6H5NH2BH2C6H5, by anhydrous pentane washed product 2-3 time.
Embodiment 10
Weigh appropriate LiAlH respectively4How boric acid, is dissolved in a certain amount of absolute ether, to LiAlH4Solution adds
A small amount of 2,2 bipyridyls make indicator, and white solution becomes crocus.Will how boric acid be dissolved in slowly is added drop-wise to LiAlH4In solution,
It is immediately generated hydrogen and solid precipitation, when working as LiAlH4When solution becomes colorless, filter mixed solution with syringe-driven filter.To
Filtrate adds and appropriate (NH4)2SO4, release a large amount of hydrogen immediately.After at room temperature reacting a period of time (1-3h), use pin
Hair style filter filtering solution, takes out major part absolute ether vacuum pump, is added thereto to a large amount of anhydrous pentane, separates out
White solid product NH3BH2C10H7。
Embodiment 11
Weigh the LiAlH of optimal proportion respectively4How boric acid (lithium aluminium hydride reduction is with how boric acid mol ratio is 5:4), is dissolved in one
In quantitative absolute ether, will how boric acid be dissolved in slowly is added drop-wise to LiAlH4In solution, it is immediately generated hydrogen and solid precipitation, when
After dripping, continuation reaction a period of time filters mixed solution to not having bubble to emerge with syringe-driven filter.In filtrate
Add the CH of boric acid equimolar amounts with how3NH3Cl, releases a large amount of hydrogen immediately.After at room temperature reacting a period of time (1-3h),
Use syringe-driven filter filtering solution, filtrate is taken out major part solvent with vacuum pump, is added thereto to anhydrous pentane, separate out
Product CH3NH2BH2C10H7, wash 2-3 time with anhydrous pentane.
Embodiment 12
By 99mg LiAlH4 and 1mg 2 in glove box, 2-bipyridyl is dissolved in 5ml absolute ether, is designated as solution A.Will
How boric acid joins in 10ml absolute ether 260mg, and stirring is allowed to dissolve, and is designated as solution B.B is slowly added drop-wise in A, the Fructus Citri tangerinae of A
Yellow deepens, and drips rear stratification, and upper strata is colourless transparent solution, and lower floor is Chinese red solid precipitation, uses a diameter of 5cm
Syringe-driven filter filter mixed liquor.88mg NH is added in water white filtrate4Cl, reacts 2h, filters, and discards solid
Body impurity.Take out major part solvent absolute ether with oil pump cold well device, be added thereto to a large amount of anhydrous pentane, obtain white
Solid NH3BH2C10H7.By anhydrous pentane washed product 2-3 time.
Embodiment 13
The LiAlH of optimal proportion is weighed in glove box4How boric acid, is dissolved in the absolute ether of appropriate amount, will how boron
Acid is dissolved in and is slowly added drop-wise to LiAlH4In solution, it is immediately generated hydrogen and solid precipitation, when continuing reaction one section after dripping
Between to not when there being bubble to emerge, filter mixed solution with syringe-driven filter.Boric acid equimolar amounts is added with how in filtrate
C6H5NH3Cl, releases a large amount of hydrogen immediately.At room temperature after reaction a period of time 2h, filter mixing with syringe-driven filter molten
Liquid, takes out major part by absolute ether vacuum pump, is added thereto to anhydrous pentane, separates out product C6H5NH2BH2C10H7.With
Anhydrous pentane washed product 2-3 time.
Claims (4)
1. the synthetic method of a B replacement ammonia borine, it is characterised in that:
Weigh organic boronic and lithium aluminium hydride reduction respectively according to mol ratio organic boronic/lithium aluminium hydride reduction=1:1-1:2, and dissolve respectively
In appropriate absolute ether, after hybrid reaction, filtering, collect filtrate, evacuation removes ether solvent, obtains product organo-borane
Lithium；
Being dissolved in absolute ether by organo-borane lithium, add ammonium salt reaction 1-3 h, filter, collect filtrate, evacuation removes second
Ether solvents, obtains product B substituted radical ammonia borine.
Synthetic method the most according to claim 1, it is characterised in that described organic boronic is alkyl borane lithium or aromatic radical
Borine lithium.
Synthetic method the most according to claim 1, it is characterised in that described boric acid is methyl-boric acid, phenylboric acid or naphthalene
Boric acid, described ammonium salt is NH4Cl、(NH4)2SO4、CH3NH3Cl or anilinechloride.
Synthetic method the most according to claim 1, it is characterised in that described boric acid is methyl-boric acid, described ammonium salt is
NH4Cl, methyl-boric acid is 1:1 with the mol ratio of ammonium chloride.
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| CN112010320A (en) * | 2020-08-12 | 2020-12-01 | 河南师范大学 | Preparation method of B-substituted sodium cyanoborohydride |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100272623A1 (en) * | 2009-04-22 | 2010-10-28 | K-Energetics Corp. | Ambient temperature liquid ammonia process for the manufacture of ammonia borane |
| WO2014028281A1 (en) * | 2012-08-14 | 2014-02-20 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of The University Of Oregon | B-alkyl-substituted ammonia boranes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20100272623A1 (en) * | 2009-04-22 | 2010-10-28 | K-Energetics Corp. | Ambient temperature liquid ammonia process for the manufacture of ammonia borane |
| WO2014028281A1 (en) * | 2012-08-14 | 2014-02-20 | State Of Oregon Acting By And Through The State Board Of Higher Education On Behalf Of The University Of Oregon | B-alkyl-substituted ammonia boranes |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112010320A (en) * | 2020-08-12 | 2020-12-01 | 河南师范大学 | Preparation method of B-substituted sodium cyanoborohydride |
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