CN107098357A - A kind of preparation method of the boronic acid compounds of octahydro three - Google Patents
A kind of preparation method of the boronic acid compounds of octahydro three Download PDFInfo
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- CN107098357A CN107098357A CN201710434718.5A CN201710434718A CN107098357A CN 107098357 A CN107098357 A CN 107098357A CN 201710434718 A CN201710434718 A CN 201710434718A CN 107098357 A CN107098357 A CN 107098357A
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- octahydro
- boronic acid
- acid compounds
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- reaction
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- 150000001642 boronic acid derivatives Chemical class 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- WUUHFRRPHJEEKV-UHFFFAOYSA-N tripotassium borate Chemical compound [K+].[K+].[K+].[O-]B([O-])[O-] WUUHFRRPHJEEKV-UHFFFAOYSA-N 0.000 claims abstract description 23
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910000085 borane Inorganic materials 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- 239000000956 alloy Substances 0.000 claims abstract description 8
- 229910003251 Na K Inorganic materials 0.000 claims abstract description 7
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 150000008040 ionic compounds Chemical class 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011734 sodium Substances 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- -1 Halide anion Chemical class 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 238000005092 sublimation method Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- 229910000574 NaK Inorganic materials 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- NSIKFNOYIGGILA-UHFFFAOYSA-N [Na].[Na].[K] Chemical compound [Na].[Na].[K] NSIKFNOYIGGILA-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- AENYAMPVQFAKHY-UHFFFAOYSA-N boric acid;potassium Chemical compound [K].OB(O)O AENYAMPVQFAKHY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002170 ethers Chemical class 0.000 claims description 2
- 150000002240 furans Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000000859 sublimation Methods 0.000 claims description 2
- 230000008022 sublimation Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 4
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- OJMOMXZKOWKUTA-UHFFFAOYSA-N aluminum;borate Chemical compound [Al+3].[O-]B([O-])[O-] OJMOMXZKOWKUTA-UHFFFAOYSA-N 0.000 description 3
- 238000012805 post-processing Methods 0.000 description 3
- 235000007686 potassium Nutrition 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 235000015424 sodium Nutrition 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- WYXIGTJNYDDFFH-UHFFFAOYSA-Q triazanium;borate Chemical compound [NH4+].[NH4+].[NH4+].[O-]B([O-])[O-] WYXIGTJNYDDFFH-UHFFFAOYSA-Q 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- AIGRXSNSLVJMEA-FQEVSTJZSA-N ethoxy-(4-nitrophenoxy)-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound O([P@@](=S)(OCC)C=1C=CC=CC=1)C1=CC=C([N+]([O-])=O)C=C1 AIGRXSNSLVJMEA-FQEVSTJZSA-N 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- CMVOJSWILFNLFI-UHFFFAOYSA-L magnesium;dibromate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-]Br(=O)=O.[O-]Br(=O)=O CMVOJSWILFNLFI-UHFFFAOYSA-L 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 229910000497 Amalgam Inorganic materials 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910000645 Hg alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910000799 K alloy Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- LFEZBRCLZFHLLA-UHFFFAOYSA-N [K].[Hg] Chemical compound [K].[Hg] LFEZBRCLZFHLLA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- QGKPFZYVJCURLK-UHFFFAOYSA-N boric acid;tetramethylazanium Chemical compound OB(O)O.C[N+](C)(C)C QGKPFZYVJCURLK-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 238000001897 boron-11 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- MHAOVLQYUNAHGO-UHFFFAOYSA-N gold mercury Chemical compound [Au].[Hg] MHAOVLQYUNAHGO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- BITPAXWTJXOWKL-UHFFFAOYSA-N lithium;oxolane Chemical compound [Li].C1CCOC1 BITPAXWTJXOWKL-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- MJGFBOZCAJSGQW-UHFFFAOYSA-N mercury sodium Chemical compound [Na].[Hg] MJGFBOZCAJSGQW-UHFFFAOYSA-N 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
- ICLVFRLZPBKZDP-UHFFFAOYSA-N potassium;sodium;hydrogen borate Chemical compound [Na+].[K+].OB([O-])[O-] ICLVFRLZPBKZDP-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001023 sodium amalgam Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- 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
- C01B35/02—Boron; Borides
- C01B35/026—Higher boron hydrides, i.e. containing at least three boron atoms
-
- 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/86—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by NMR- or ESR-data
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
Abstract
The invention belongs to technical field of material, specially a kind of preparation method of the boronic acid compounds of octahydro three.The present invention prepares the potassium borate of octahydro three using Borane solution and the step of Na-K alloy synthesis under normal pressure one；Then, the potassium borate of octahydro three and ionic compound ball-milling reaction are produced the corresponding boronic acid compounds of octahydro three.The inventive method is simple to operate, and product purity is high, and cost is relatively low, is produced on a large scale.
Description
Technical field
The invention belongs to technical field of material, and in particular to the preparation method of the boronic acid compounds of octahydro three.
Background technology
The boronic acid compounds of octahydro three are the important compounds of a class.The material can replace borine and boron hydride ion
Compound prepares the raw material of more senior borine；Metal boride film can be prepared as presoma；Tried as excellent reproducibility
Agent, can reduce a series of carbon-based organic matters；Meanwhile, they have high hydrogen content, can be used as the additive of propellant.
The preparation of the borate of octahydro three is the important step for restricting such Materials all the time, is also that association area is ground
The key point studied carefully.The preparation method of a variety of borates of octahydro three is had reported at present：Such as use metal（Na, K, Rb, Cs）With
The alloy of mercury formation reacts with diborane or pentaborane；Sodium hydride, sodium borohydride, sodium amalgam and tetraborane react；Or
Pentaborane, decaborane cracking are obtained.Wherein, there is the reaction that earliest method is Metallic amalgam and diborane, nineteen twenty-three
Afred Stock et al. report the reaction first, but it is Na to be originally mistakenly considered product2B2H6, by by A.E. Newkirk and
Hough, W.V et al. repetition experiment determine product final form for NaB3H8Ether complexes；Subsequent nineteen fifty-nine Parry,
R.W. tetraborane and sodium hydride reaction generation NaB are utilized with L.J. Edwards3H8；J. M. Makhlouf in 1967 etc. are again
KB is prepared for iodate nak response in hot acetonitrile by the boric acid tetramethyl-ammonium of octahydro three3H8；Paxshall in 1974, G.W are detailed
Carefully describe sodium borohydride and iodine or BFEE is prepared for NaB3H8Ether complexes；Hill in 1991 et al. passes through
KB has been made with Borane solution reaction in potassium mercury alloy3H8；Gregory S. Girolami are with NaB within 20043H8For presoma into
Work(has synthesized Cr (B3H8)2.These methods, due to having used the extremely toxic substances such as senior borine, mercury metal, technological requirement condition is high,
Product complex separations are difficult, and economy, security are poor.Therefore, new type of safe, the need of the economic borate synthetic method of octahydro three
Ask still urgent.
The more other boronic acid compounds of octahydro three of the potassium borate of octahydro three, such as Boratex of octahydro three, the lithium borate of octahydro three, octahydro three
Antifungin etc. has the advantages that to be easily isolated, not with common solvent complexing, stable.Meanwhile, can as raw material using the potassium borate of octahydro three
To prepare the serial borate family compound of octahydro three.Thus, the preparation method of the potassium borate of octahydro three is studied, and using it as starting material
Prepare the preparation technology route that the serial boronic acid compounds of octahydro three are the more practical boronic acid compounds of octahydro three.
The content of the invention
It is an object of the invention to provide a kind of preparation technology is simple, reaction condition gentle, and the octahydro three that can be synthesized in batches
The preparation method of boronic acid compounds.
The preparation method for the boronic acid compounds of octahydro three that the present invention is provided, is concretely comprised the following steps：
（1）First, Borane solution and Na-K alloy synthesis under normal pressure are generated into the boric acid potassium solution of octahydro three, located after the solution is carried out
Reason, obtains the solvent-free potassium borate solid of pure octahydro three；
（2）Then, the potassium borate of octahydro three and other ionic compound solid-phase ball millings are reacted；It is molten using solvent after reaction terminates
Take or sublimation method extracts the boronic acid compounds of product octahydro three.
Step of the present invention（1）In, when preparing three potassium borate sodium of octahydro, reacted using Na-K alloy and borine, wherein sodium potassium
Alloy is liquid in respective reaction temperature, and Na-K alloy is directly mixed to prepare by metallic sodium with metallic potassium, wherein the content of sodium
Account for the 1%-10% of gross mass；
Borane solution is commercially available prod, or passes through metal halide MXnWith the obtained solution of sodium borohydride reaction.Use Liquid Sodium
Potassium-sodium alloy can be effectively ensured the reaction of potassium and borine and is fully smoothed out in normal temperature, normal pressure, it is to avoid use highly toxic mercury gold
The complicated postprocessing working procedures for belonging to and being induced by it, make reaction more quick, cleaning.
Step of the present invention（1）In, during synthesis under normal pressure generation three potassium borate of octahydro, the temperature of reaction is -10 ~ 60 DEG C, reaction
Time is 1-12h, and reaction atmosphere is inert gas N2, Ar or He, reacting system pressure are persistently to stir in normal pressure, course of reaction
Mix.
Step of the present invention（1）In, the post processing includes filtering, concentration, appropriate solvent washing, and pure octahydro three is finally made
Potassium borate solid.Specifically, post-processing operation can be：First by reacting liquid filtering, filtrate is removed after solvent, addition ether,
The mixed solvent of dichloromethane, dichloromethane and acetonitrile separates out product, and separation obtains precipitate, then obtains solvent-free through drying
The potassium borate of octahydro three.
Step of the present invention（2）In, when preparing other three boronic acid compounds of octahydro, the potassium borate of octahydro three is used for starting material,
By itself and separation and Extraction product after corresponding ionic compound solid phase reaction.This method has preferable applicability, and product is solvent-free
The boronic acid compounds of octahydro three, or the borate of octahydro three and the complex compound of solvent coordination.Wherein, the sun of other ionic compounds
Ion is selected from：Li+, Na+, Cs+, Ca2+, Mg2+, Al3+, Ti3+, Cr2+, Co2+, Ni2+, Fe2+, Mn2+, Zn2+, NH4 +, R4N+, R3S+, R4P+Deng it is one or more of compound；Anion is selected from：Halide anion, sulfate radical, phosphate radical, nitric acid
Root, the anion that acetate etc. can be with above-mentioned cation formation stable compound；R group is the alkyl or virtue of 1 to 4 carbon atom
Perfume base group.
Step of the present invention（2）In, crude product is taken out in particular atmosphere, is taken or sublimation method extraction product using solvent is molten
The boronic acid compounds of octahydro three；The solvent is mainly selected from water, ammonia, amine, hydro carbons, ethers, furans etc., the production that solvent extraction is obtained
Thing is the compound being coordinated containing solvent molecule；Distillation is carried out in inert atmosphere or vacuum, and sublimation temperature is not higher than 150 DEG C,
For example, 30-150 DEG C.It is solvent free compound that obtained product is extracted in distillation.
The preparation method advantage of the boronic acid compounds of octahydro three of the present invention is that preparation technology is simpler, reaction condition temperature
With, be not related to HTHP operation, and poisonous mercury metal and senior borine use, moderate cost, available for relatively large product
Preparation.
Brief description of the drawings
The potassium borate of Fig. 1 octahydros three11B NMR spectras.
The XRD results of the potassium borate of Fig. 2 octahydros three.
The XRD results of the ammonium borate of Fig. 3 octahydros three.
The tetrahydrofuran of the lithium borate of Fig. 4 octahydros three and the XRD results of ammino-complex.
The XRD results of the aluminium borate ammino-complex of Fig. 5 octahydros three.
Embodiment
Embodiment 1：The synthesis of the potassium borate of octahydro three
35.6g CuCl and 11.4gNaBH are added in 500ml branch mouthful bottles4, 200ml anhydrous tetrahydro furans are transferred to, 40 are placed in
Heated in DEG C water-bath.After four hours of stirring reaction, filtering obtains borine tetrahydrofuran solution.Weigh 7.5g metallic potassiums and
0.83g metallic sodiums obtain homogeneous silver color liquid after fully rocking mixing, are transferred on 200ml in 500ml branch mouthful eggplant-shape bottles
Borane solution is stated, is sufficiently stirred at room temperature after 10 hours, is stood, supernatant liquor is shifted, and it is solid with tetrahydrofuran wash residual
Body, washing gained clear liquid is merged, solvent is extracted, obtains white solid product.This white solid is added into ether, fully shake
Swing, it is observed that white precipitate, clear liquid is filtered out, then is repeatedly washed with ether, it is octahydro three to obtain 3.2g white precipitates
Potassium borate.Its11BNMR and XRD results are shown in Fig. 1 and Fig. 2.
Embodiment 2：The synthesis of the ammonium borate of octahydro three
Weigh the potassium borate 1g of octahydro three and 1.37g NH of preparation4Cl is put into a certain amount of steel ball, rotating speed 500rpm in ball grinder
Lower ball milling 3 hours.Solid after ball milling is collected and is placed in 100ml reaction bulbs, 20ml acetonitriles is added, fully rocks, can see
Occur to white precipitate, acetonitrile clear liquid is filtered out under nitrogen protection, drained, can obtain the ammonium borate solid of octahydro three of white.
Its XRD is shown in Fig. 3.
Embodiment 3：The synthesis of the tetrahydrofuran complex and ammino-complex of the lithium borate of octahydro three
The potassium borate 1g of octahydro three and 1.09g LiCl of preparation are weighed in ball grinder, a certain amount of steel ball, rotating speed 400rpm is put into
Lower ball milling 3 hours, the solid after ball milling is collected and is placed in 100ml reaction bulbs, is added 20ml tetrahydrofurans, is fully rocked, can
To see that white precipitate occurs, tetrahydrofuran clear liquid is filtered out under nitrogen protection, drained, can obtain the boric acid of octahydro three of white
Lithium tetrahydrofuran solid.Its XRD is shown in Fig. 4.Above-mentioned reaction solution is changed to liquefied ammonia, reacted 4 hours at -78 DEG C, and carry out phase
It should handle, can obtain the ammino-complex solid of the lithium borate of octahydro three of white.Its XRD is shown in Fig. 4.
Embodiment 4：The synthesis of the aluminium borate ammino-complex of octahydro three
Weigh the potassium borate 1g of octahydro three and 1.13g AlCl of preparation3In 100ml reaction bulbs, ammonia is passed through at -78 DEG C, and
It is sufficiently stirred for 3 hours, it was observed that white precipitate is generated, at low temperature filters out liquefied ammonia clear liquid, and be dried under vacuum, obtains white
The aluminium borate ammino-complex of octahydro three of color, its XRD is shown in Fig. 5.
Embodiment 5：The synthesis of the antifungin of octahydro three
Weigh the potassium borate 1g of octahydro three and 2.34g MgBr of preparation2In ball grinder, a certain amount of steel ball, rotating speed 400rpm are put into
Lower ball milling 3 hours, the solid after ball milling is collected and is placed in 100ml reaction bulbs, -20 DEG C of cold pipes is inserted under nitrogen atmosphere, simultaneously
Heating response bottle, is evacuated to below 0.05Torr, white Mg (B is collected in cold tube portion at 80 DEG C3H8)2Solid.
Claims (6)
1. a kind of preparation method of the boronic acid compounds of octahydro three, it is characterised in that concretely comprise the following steps：
（1）First, Borane solution and Na-K alloy synthesis under normal pressure are generated into the boric acid potassium solution of octahydro three, located after the solution is carried out
Reason, obtains the solvent-free potassium borate solid of pure octahydro three；
（2）Then, the potassium borate of octahydro three and other ionic compounds are carried out solid-phase ball milling reaction；After reaction terminates, using molten
Agent is molten to be taken or the boronic acid compounds of sublimation method extraction product octahydro three.
2. the preparation method of the boronic acid compounds of octahydro three according to right wants 1, it is characterised in that step（1）In, use sodium
Potassium-sodium alloy reacts with borine, and Na-K alloy is liquid in respective reaction temperature, and Na-K alloy is direct with metallic potassium by metallic sodium
It is mixed to prepare, the content of wherein sodium accounts for the 1%-10% of gross mass.
3. the preparation method of the boronic acid compounds of octahydro three according to right wants 1, it is characterised in that step（1）In, atmospheric reverse
When should generate three potassium borate of octahydro, the temperature of reaction is -10-60 DEG C, and the reaction time is 1-12h, and reaction atmosphere is inert gas
N2, Ar or He are persistently stirred in course of reaction.
4. the preparation method of the boronic acid compounds of octahydro three according to right wants 1, it is characterised in that step（1）In, it is described after
Processing includes filtering, concentration, appropriate solvent washing, and the pure potassium borate solid of octahydro three is finally made.
5. the preparation method of the boronic acid compounds of octahydro three according to right wants 1, it is characterised in that step（2）In, it is described its
Its ionic compound, cation is selected from：Li+, Na+, Cs+, Ca2+, Mg2+, Al3+, Ti3+, Cr2+, Co2+, Ni2+, Fe2 +, Mn2+, Zn2+, NH4 +, R4N+, R3S+, R4P+It is one or more of compound；Anion is selected from：Halide anion, sulfuric acid
Root, phosphate radical, nitrate anion, the anion that acetate can be with above-mentioned cation formation stable compound；R group is 1 to 4 carbon original
The alkyl or aromatic group of son.
6. the preparation method of the boronic acid compounds of octahydro three according to right wants 1, it is characterised in that step（2）In, using molten
When product three boronic acid compounds of octahydro are extracted in agent, solvent for use is selected from water, ammonia, amine, hydro carbons, ethers, furans, and solvent extraction is obtained
The portion of product arrived is the compound being coordinated containing solvent molecule；When product three boronic acid compounds of octahydro are extracted in distillation, in inertia
Carried out in atmosphere or vacuum, sublimation temperature is not higher than 150 DEG C, and it is solvent free compound that obtained product is extracted in distillation.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100255A (en) * | 1985-04-01 | 1986-07-16 | 武汉大学 | The replacement(metathesis)reaction preparation method of octahydro three ammonium borates |
| CN85100254A (en) * | 1985-04-01 | 1986-08-06 | 武汉大学 | The preparation of octahydro three potassium borates and derivative thereof |
| CN106698346A (en) * | 2017-02-17 | 2017-05-24 | 河南师范大学 | Method for synthesizing anionic potassium hydroborate KB3H8 |
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2017
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85100255A (en) * | 1985-04-01 | 1986-07-16 | 武汉大学 | The replacement(metathesis)reaction preparation method of octahydro three ammonium borates |
| CN85100254A (en) * | 1985-04-01 | 1986-08-06 | 武汉大学 | The preparation of octahydro three potassium borates and derivative thereof |
| CN106698346A (en) * | 2017-02-17 | 2017-05-24 | 河南师范大学 | Method for synthesizing anionic potassium hydroborate KB3H8 |
Non-Patent Citations (2)
| Title |
|---|
| DEAN M. GOEDDE ET AL.: "A New Class of CVD Precursors to Metal Borides: Cr(B3H8)2 and Related Octahydrotriborate Complexes", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| DEAN M. GOEDDE ET AL.: "Synthesis and Characterization of the Homoleptic Octahydrotriborate Complex Cr(B3H8)2 and Its Lewis Base Adducts", 《INORGANIC CHEMISTRY》 * |
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