CN107446003A - A kind of preparation method of 3-sec-butyl lithium borohydride - Google Patents
A kind of preparation method of 3-sec-butyl lithium borohydride Download PDFInfo
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- CN107446003A CN107446003A CN201610379585.1A CN201610379585A CN107446003A CN 107446003 A CN107446003 A CN 107446003A CN 201610379585 A CN201610379585 A CN 201610379585A CN 107446003 A CN107446003 A CN 107446003A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 126
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims abstract description 61
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims abstract description 38
- 239000012280 lithium aluminium hydride Substances 0.000 claims abstract description 37
- ZUVQXWUBMQNMGL-UHFFFAOYSA-N butan-2-ylboron Chemical compound [B]C(C)CC ZUVQXWUBMQNMGL-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical compound [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 7
- 229910010084 LiAlH4 Inorganic materials 0.000 claims abstract description 4
- 229910000091 aluminium hydride Inorganic materials 0.000 claims abstract description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 165
- 239000000243 solution Substances 0.000 claims description 143
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 86
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 37
- 239000011259 mixed solution Substances 0.000 claims description 22
- 229910015900 BF3 Inorganic materials 0.000 claims description 20
- -1 bromo isobutyl Chemical group 0.000 claims description 18
- UWTDFICHZKXYAC-UHFFFAOYSA-N boron;oxolane Chemical compound [B].C1CCOC1 UWTDFICHZKXYAC-UHFFFAOYSA-N 0.000 claims description 16
- QBNJPSHRAWSBDW-UHFFFAOYSA-N 2-methylpropane;hydrobromide Chemical compound Br.CC(C)C QBNJPSHRAWSBDW-UHFFFAOYSA-N 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 14
- 239000005457 ice water Substances 0.000 claims description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- MOFPNEADTSBYFQ-UHFFFAOYSA-N tributan-2-yl borate Chemical compound CCC(C)OB(OC(C)CC)OC(C)CC MOFPNEADTSBYFQ-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 claims 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 3
- HLVFKOKELQSXIQ-UHFFFAOYSA-N 1-bromo-2-methylpropane Chemical compound CC(C)CBr HLVFKOKELQSXIQ-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000012448 Lithium borohydride Substances 0.000 description 2
- OEHCXDNEGABFEZ-UHFFFAOYSA-N O1CCCC1.[Li].[AlH3] Chemical compound O1CCCC1.[Li].[AlH3] OEHCXDNEGABFEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- 239000008896 Opium Substances 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000005695 dehalogenation reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229940005483 opioid analgesics Drugs 0.000 description 1
- 229960001027 opium Drugs 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of preparation method of 3-sec-butyl lithium borohydride, including three sec-butyl boron preparation processes, reactant configuration step, 3-sec-butyl lithium borohydride preparation process, it is characterised in that in the three sec-butyls boron preparation process, preparing reaction process principle is:3Mg+BF3·Et2O+3C4H9Br=(C4H9)3B+3MgBrF, in the 3-sec-butyl lithium borohydride preparation process, preparing reaction process principle is:(C4H9)3B+LiAlH4+C6H12N=Li (C4H9)3BH+AlH3·C6H12N.Its advantage is:TED A can be generated with aluminum hydride by adding triethylene diamine (TED)lH3White precipitate removes from system, avoids reaction from developing to second step.So as to obtain 3-sec-butyl lithium borohydride.
Description
Technical field
The present invention relates to field of inorganic chemical engineering, particularly a kind of preparation method of 3-sec-butyl lithium borohydride.
Background technology
3-sec-butyl lithium borohydride:Molecular formula:LiB[CH(CH3)CH2CH3]3H,CAS:38721-52-7, molecular weight
190.11, density 0.89g/ml, flash-point are -17 DEG C, and the business form of this product is dissolved in the molar solution in tetrahydrofuran.
This product is widely used as the strong reductant of gentle highly-solid selectively in organic synthesis, and the asymmetric selective reduction for ketone obtains
To alcohol, it can also be used to which enol Isosorbide-5-Nitrae conjugate addition reduces to obtain ketone or alcohol, is total to for the fine derivative of propylene outside selective reduction ring
Yoke double bond and iodide, for two fat, the monocyclic pyrimidine of dehalogenation, 5- trimethylsilyls bar are reset because of the N- methoxy carbonyls with deprotection
In the opioids substitution N- non-opium reactions of base, it is that one kind effectively removes meso reagent, under cryogenic, can be had
Effect reduction conjugated carbonyl compound.It is mainly used in medical industry, perfume industry.
Research shows that lithium aluminium hydride reduction can react three Zhong Ding of generation in subzero 10 degree of tetrahydrofuran with three sec-butyl boron
Base boron hydride, but the aluminum hydride of product three of paying generated will react with 3-sec-butyl lithium borohydride and generates new chemical combination again
Thing, the final product of reaction be not it is desirable that 3-sec-butyl lithium borohydride.
The content of the invention
The invention aims to solve the above problems, a kind of preparation method of 3-sec-butyl lithium borohydride is devised.
Specific design scheme is:
A kind of preparation method of 3-sec-butyl lithium borohydride, including three sec-butyl boron preparation processes, reactant configuration step,
3-sec-butyl lithium borohydride preparation process, it is characterised in that
In the three sec-butyls boron preparation process, preparing reaction process principle is:
3Mg+BF3·Et2O+3C4H9Br=(C4H9)3B+3MgBrF,
In the 3-sec-butyl lithium borohydride preparation process, preparing reaction process principle is:
(C4H9)3B+LiAlH4+C6H12N=Li (C4H9)3BH+AlH3·C6H12N。
In the three sec-butyls boron preparation process,
Isobutane bromide is mixed with absolute ether, and is stirred, mixing time 5min, configuration obtains bromo
Iso-butane diethyl ether solution,
The isobutane bromide of the addition and the mass fraction of absolute ether are 46.5 parts of isobutane bromide, absolute ether 88
Part,
Metal magnesium powder is mixed with boron trifluoride ether solution, and adds absolute ether, configuration obtains mixed solution,
In the mixed solution, the mass fraction for adding metal magnesium powder and boron trifluoride ether solution is metal magnesium powder 46.5
Part, 88 parts of boron trifluoride ether solution,
The concentration of the boron trifluoride ether solution is 1.158g/ml.
In the mixed solution, the volume parts for adding boron trifluoride ether solution and ether are respectively BFEE
76 parts of solution, 500 parts of absolute ether.
Isobutane bromide diethyl ether solution is instilled in the mixed solution by constant pressure funnel, it is quiet after stirring 90-150min
Put 12h,
Supernatant is taken after staticly settling, then precipitated liquid is washed with ether, cleaning solution is reclaimed, collects the supernatant
With cleaning solution, three sec-butyl borate ether solution are obtained,
Because three sec-butyl boron chemisms are very active, air vigorous combustion, therefore the three sec-butyl boron distilled out are met
It must flow directly into tetrahydrofuran solution, to be allowed to no longer ingress of air, tetrahydrofuran plays protection to three sec-butyl boron and made
With.
Three sec-butyl borate ether solution are distilled, obtain three sec-butyl boron, and its water conservancy diversion is entered into tetrahydrofuran solution
In, obtain three sec-butyl boron tetrahydrofuran solutions.
In reactant configuration step,
Lithium aluminium hydride reduction is stirred with tetrahydrofuran and mixed, configuration obtains lithium aluminium hydride reduction tetrahydrofuran solution,
The mixed process of the lithium aluminium hydride reduction and tetrahydrofuran is carried out in ice-water bath,
The concentration of the lithium aluminium hydride reduction tetrahydrofuran solution is 1mol/L,
The three sec-butyls boron tetrahydrofuran solution is diluted, purified, it is the three secondary of 1mol/L that configuration, which obtains concentration,
Butyl boron tetrahydrofuran solution,
Triethylene diamine and tetrahydrofuran are stirred, configuration concentration is that 1mol/L triethylene diamine tetrahydrofuran is molten
Liquid,
In 3-sec-butyl lithium borohydride preparation process,
The three sec-butyls boron tetrahydrofuran solution is mixed with triethylene diamine tetrahydrofuran solution, and is passed through nitrogen
Gas is stirred,
The mixing of the three sec-butyls boron tetrahydrofuran solution and triethylene diamine tetrahydrofuran solution, whipping step need to be
Carried out in ice-water bath,
By ice-water bath, make the mixing of the three sec-butyls boron tetrahydrofuran solution and triethylene diamine tetrahydrofuran solution
Solution is cooled to 0 DEG C,
The lithium aluminium hydride reduction tetrahydrofuran solution is instilled into the three sec-butyls boron tetrahydrofuran solution and triethylene diamine
In the mixed solution of tetrahydrofuran solution, 3-sec-butyl lithium borohydride mixed solution is obtained,
Add three sec-butyl boron tetrahydrofuran solutions, triethylene diamine tetrahydrofuran solution, instill lithium aluminium hydride reduction tetrahydrochysene furan
The volume parts ratio of solution of muttering is three sec-butyl boron tetrahydrofuran solutions:Triethylene diamine tetrahydrofuran solution:Instill aluminum hydride
Lithium tetrahydrofuran solution=1:1:1,
During the dropwise addition of the lithium aluminium hydride reduction tetrahydrofuran solution, it need to be stirred,
In the dropwise addition volume and the parts by volume of three sec-butyl boron tetrahydrofuran solutions of the lithium aluminium hydride reduction tetrahydrofuran solution
Number is than being 2.5:When 0.5, white suspension thing need to be produced,
After the lithium aluminium hydride reduction tetrahydrofuran solution is added dropwise to complete, continue to stir 25-35min,
The 3-sec-butyl lithium borohydride mixed solution is filtered by the filter of 800 mesh, obtained colourless
Bright 3-sec-butyl lithium borohydride tetrahydrofuran solution,
The 3-sec-butyl lithium borohydride tetrahydrofuran solution is distilled, obtains three sec-butyls that concentration is 1mol/L
Lithium borohydride tetrahydrofuran solution.
The preparation method of the 3-sec-butyl lithium borohydride obtained by the above-mentioned technical proposal of the present invention, its advantage
It is:
TED-AlH can be generated with aluminum hydride by adding triethylene diamine (TED)3White precipitate removes from system, avoids
React and develop to second step.So as to obtain 3-sec-butyl lithium borohydride.
Embodiment
The present invention is specifically described below.
A kind of preparation method of 3-sec-butyl lithium borohydride, including three sec-butyl boron preparation processes, reactant configuration step,
3-sec-butyl lithium borohydride preparation process, it is characterised in that
In the three sec-butyls boron preparation process, preparing reaction process principle is:
3Mg+BF3·Et2O+3C4H9Br=(C4H9)3B+3MgBrF,
In the 3-sec-butyl lithium borohydride preparation process, preparing reaction process principle is:
(C4H9)3B+LiAlH4+C6H12N=Li (C4H9)3BH+AlH3·C6H12N。
In the three sec-butyls boron preparation process,
Isobutane bromide is mixed with absolute ether, and is stirred, mixing time 5min, configuration obtains bromo
Iso-butane diethyl ether solution,
The isobutane bromide of the addition and the mass fraction of absolute ether are 46.5 parts of isobutane bromide, absolute ether 88
Part,
Metal magnesium powder is mixed with boron trifluoride ether solution, and adds absolute ether, configuration obtains mixed solution,
In the mixed solution, the mass fraction for adding metal magnesium powder and boron trifluoride ether solution is metal magnesium powder 46.5
Part, 88 parts of boron trifluoride ether solution,
The concentration of the boron trifluoride ether solution is 1.158g/ml.
In the mixed solution, the volume parts for adding boron trifluoride ether solution and ether are respectively BFEE
76 parts of solution, 500 parts of absolute ether.
Isobutane bromide diethyl ether solution is instilled in the mixed solution by constant pressure funnel, it is quiet after stirring 90-150min
Put 12h,
Supernatant is taken after staticly settling, then precipitated liquid is washed with ether, cleaning solution is reclaimed, collects the supernatant
With cleaning solution, three sec-butyl borate ether solution are obtained,
Because three sec-butyl boron chemisms are very active, air vigorous combustion, therefore the three sec-butyl boron distilled out are met
It must flow directly into tetrahydrofuran solution, to be allowed to no longer ingress of air, tetrahydrofuran plays protection to three sec-butyl boron and made
With.
Three sec-butyl borate ether solution are distilled, obtain three sec-butyl boron, and its water conservancy diversion is entered into tetrahydrofuran solution
In, obtain three sec-butyl boron tetrahydrofuran solutions.
In reactant configuration step,
Lithium aluminium hydride reduction is stirred with tetrahydrofuran and mixed, configuration obtains lithium aluminium hydride reduction tetrahydrofuran solution,
The mixed process of the lithium aluminium hydride reduction and tetrahydrofuran is carried out in ice-water bath,
The concentration of the lithium aluminium hydride reduction tetrahydrofuran solution is 1mol/L,
The three sec-butyls boron tetrahydrofuran solution is diluted, purified, it is the three secondary of 1mol/L that configuration, which obtains concentration,
Butyl boron tetrahydrofuran solution,
Triethylene diamine and tetrahydrofuran are stirred, configuration concentration is that 1mol/L triethylene diamine tetrahydrofuran is molten
Liquid,
In 3-sec-butyl lithium borohydride preparation process,
The three sec-butyls boron tetrahydrofuran solution is mixed with triethylene diamine tetrahydrofuran solution, and is passed through nitrogen
Gas is stirred,
The mixing of the three sec-butyls boron tetrahydrofuran solution and triethylene diamine tetrahydrofuran solution, whipping step need to be
Carried out in ice-water bath,
By ice-water bath, make the mixing of the three sec-butyls boron tetrahydrofuran solution and triethylene diamine tetrahydrofuran solution
Solution is cooled to 0 DEG C,
The lithium aluminium hydride reduction tetrahydrofuran solution is instilled into the three sec-butyls boron tetrahydrofuran solution and triethylene diamine
In the mixed solution of tetrahydrofuran solution, 3-sec-butyl lithium borohydride mixed solution is obtained,
Add three sec-butyl boron tetrahydrofuran solutions, triethylene diamine tetrahydrofuran solution, instill lithium aluminium hydride reduction tetrahydrochysene furan
The volume parts ratio of solution of muttering is three sec-butyl boron tetrahydrofuran solutions:Triethylene diamine tetrahydrofuran solution:Instill aluminum hydride
Lithium tetrahydrofuran solution=1:1:1,
During the dropwise addition of the lithium aluminium hydride reduction tetrahydrofuran solution, it need to be stirred,
In the dropwise addition volume and the parts by volume of three sec-butyl boron tetrahydrofuran solutions of the lithium aluminium hydride reduction tetrahydrofuran solution
Number is than being 2.5:When 0.5, white suspension thing need to be produced,
After the lithium aluminium hydride reduction tetrahydrofuran solution is added dropwise to complete, continue to stir 25-35min,
The 3-sec-butyl lithium borohydride mixed solution is filtered by the filter of 800 mesh, obtained colourless
Bright 3-sec-butyl lithium borohydride tetrahydrofuran solution,
The 3-sec-butyl lithium borohydride tetrahydrofuran solution is distilled, obtains three sec-butyls that concentration is 1mol/L
Lithium borohydride tetrahydrofuran solution.
Embodiment 1
1000ml there-necked flasks are taken, add isobutane bromide 256g, (closing 203ml) and 170ml absolute ethers, are stirred 5 minutes,
It is standby.
Absolute ether 500ml is added in 1000ml, adds metal magnesium powder 46.5g, adds boron trifluoride ether solution 88g
(closing 76ml), starts stirring.
The isobutane bromide diethyl ether solution prepared is added in constant pressure funnel, is slowly dropped in above-mentioned there-necked flask,
Rate of addition is advisable with aether backflow, must not be too fast.
After the diethyl ether solution of isobutane bromide drips, continue stirring 2 hours, supernatant is poured out after placing 12 hours.
The sediment after the supernatant poured out is subjected to secondary washing with ether again, reclaims cleaning solution, reaction is waits ought
Carried out under conditions of amount, any raw material all cannot be excessive, otherwise causes impurity too many, have impact on the quality of product.
Prepare three sec-butyl boron examples
For experiment 7 and 8, due to ether addition very little, solution becomes very thick, and stirring is extremely difficult.Work as ether
When addition is more, although not influenceed too much on reaction, trouble is added for follow-up distillation ether, improves energy consumption
Embodiment 2
A, 1mol/L lithium aluminium hydride reduction tetrahydrofuran solutions are configured
In a 1000ml recorder jar, 500ml tetrahydrofurans are added, are placed in ice-water bath.It is slowly added to 37.95g hydrogen
Change aluminium lithium, then be poured slowly into tetrahydrofuran to 1000ml, placed with glass bar stirring stand-by.
B, the sec-butyl boron tetrahydrofuran solutions of 1mol/L tri- are configured
In 1000ml recorder jar, the tetrahydrofuran solution containing the sec-butyl boron of 182.16g tri- is added, is added
Tetrahydrofuran stirs set aside for use to 1000ml with glass bar.
C, 1mol/L triethylene diamine tetrahydrofuran solutions are configured.
In 1000ml recorder jars, 500ml tetrahydrofuran solutions are added, add 112.18g triethylene diamines,
Tetrahydrofuran is poured into again to 1000ml, is stirred with glass bar, it is stand-by until triethylene diamine is completely dissolved.
Experimental implementation
In 3000ml there-necked flasks, the tetrahydrofuran solution of the 1000ml sec-butyl boron of 1mol/L tri- is added, is added simultaneously
1000ml 1mol/L triethylene diamine tetrahydrofuran solutions, are passed through nitrogen and start to stir, the mixed liquid of the two in ice-water bath
0 DEG C is cooled to, 1000ml 1mol/L lithium aluminium hydride reduction tetrahydrofuran solution is slowly dropped to above-mentioned mixing with constant pressure funnel
In liquid, time for adding about 10 hours.All it be preferably must be held in during whole be added dropwise in ice-water bath.When being added dropwise to about 500ml
During lithium aluminium hydride reduction tetrahydrofuran solution, there is white suspension thing in solution, the appearance of white suspension thing is that the feature of this experiment shows
As if not occurring white suspension thing in an experiment, illustrating that this experiment is unsuccessful.Lithium aluminium hydride reduction tetrahydrofuran solution is added
Afterwards, continue to stir half an hour, filtered in the filter of 800 mesh, obtain colourless transparent liquid, be detected as a 0.32mol/L left sides
Right product, substantially near theoretical value.
The preparation experiment of 3-sec-butyl lithium borohydride
The 3-sec-butyl lithium borohydride tetrahydrofuran solution of filtering is heated into distillation, steams about 68% tetrahydrofuran,
Obtain finished product 1mol/L or so 3-sec-butyl lithium borohydride tetrahydrofuran solution.Concentration is 1.03mol/L or so after testing.
Above-mentioned technical proposal only embodies the optimal technical scheme of technical solution of the present invention, those skilled in the art
Some variations that some of which part may be made are embodied the present invention principle, belong to protection scope of the present invention it
It is interior.
Claims (4)
1. a kind of preparation method of 3-sec-butyl lithium borohydride, including three sec-butyl boron preparation processes, reactant configuration step, three
Sec-butyl lithium borohydride preparation process, it is characterised in that
In the three sec-butyls boron preparation process, preparing reaction process principle is:
3Mg+BF3·Et2O+3C4H9Br=(C4H9)3B+3MgBrF,
In the 3-sec-butyl lithium borohydride preparation process, preparing reaction process principle is:
(C4H9)3B+LiAlH4+C6H12N=Li (C4H9)3BH+AlH3·C6H12N。
2. according to the preparation method of the 3-sec-butyl lithium borohydride described in claim 1, it is characterised in that three sec-butyl
In boron preparation process,
Isobutane bromide is mixed with absolute ether, and is stirred, mixing time 5min, configuration obtains bromo isobutyl
Alkane diethyl ether solution,
The isobutane bromide of the addition and the mass fraction of absolute ether are 46.5 parts of isobutane bromide, 88 parts of absolute ether,
Metal magnesium powder is mixed with boron trifluoride ether solution, and adds absolute ether, configuration obtains mixed solution,
In the mixed solution, the mass fraction that adds metal magnesium powder and boron trifluoride ether solution is 46.5 parts of metal magnesium powder,
88 parts of boron trifluoride ether solution,
The concentration of the boron trifluoride ether solution is 1.158g/ml.
In the mixed solution, the volume parts for adding boron trifluoride ether solution and ether are respectively boron trifluoride ether solution
76 parts, 500 parts of absolute ether.
Isobutane bromide diethyl ether solution is instilled in the mixed solution by constant pressure funnel, stood after stirring 90-150min
12h,
Supernatant is taken after staticly settling, then precipitated liquid is washed with ether, cleaning solution is reclaimed, collects the supernatant with washing
Liquid is washed, obtains three sec-butyl borate ether solution,
Three sec-butyl borate ether solution are distilled, obtain three sec-butyl boron, and its water conservancy diversion is entered in tetrahydrofuran solution, are obtained
Obtain three sec-butyl boron tetrahydrofuran solutions.
3. according to the preparation method of the 3-sec-butyl lithium borohydride described in claim 2, it is characterised in that reactant configuration step
In rapid,
Lithium aluminium hydride reduction is stirred with tetrahydrofuran and mixed, configuration obtains lithium aluminium hydride reduction tetrahydrofuran solution,
The mixed process of the lithium aluminium hydride reduction and tetrahydrofuran is carried out in ice-water bath,
The concentration of the lithium aluminium hydride reduction tetrahydrofuran solution is 1mol/L,
The three sec-butyls boron tetrahydrofuran solution is diluted, purified, configuration obtains three sec-butyls that concentration is 1mol/L
Boron tetrahydrofuran solution,
Triethylene diamine and tetrahydrofuran are stirred, configuration concentration is 1mol/L triethylene diamine tetrahydrofuran solution.
4. according to the preparation method of the 3-sec-butyl lithium borohydride described in claim 3, it is characterised in that three sec-butyl boron hydrogen
Change in lithium preparation process,
The three sec-butyls boron tetrahydrofuran solution is mixed with triethylene diamine tetrahydrofuran solution, and is passed through nitrogen and enters
Row stirring,
The mixing of the three sec-butyls boron tetrahydrofuran solution and triethylene diamine tetrahydrofuran solution, whipping step need to be in frozen water
Carried out in bath,
By ice-water bath, make the mixed solution of the three sec-butyls boron tetrahydrofuran solution and triethylene diamine tetrahydrofuran solution
0 DEG C is cooled to,
The lithium aluminium hydride reduction tetrahydrofuran solution is instilled into the three sec-butyls boron tetrahydrofuran solution and triethylene diamine tetrahydrochysene
In the mixed solution of tetrahydrofuran solution, 3-sec-butyl lithium borohydride mixed solution is obtained,
It is molten to add three sec-butyl boron tetrahydrofuran solutions, triethylene diamine tetrahydrofuran solution, instillation lithium aluminium hydride reduction tetrahydrofuran
The volume parts ratio of liquid is three sec-butyl boron tetrahydrofuran solutions:Triethylene diamine tetrahydrofuran solution:Instill lithium aluminium hydride reduction four
Hydrogen tetrahydrofuran solution=1:1:1,
During the dropwise addition of the lithium aluminium hydride reduction tetrahydrofuran solution, it need to be stirred,
In the dropwise addition volume and the volume parts ratio of three sec-butyl boron tetrahydrofuran solutions of the lithium aluminium hydride reduction tetrahydrofuran solution
For 2.5:When 0.5, white suspension thing need to be produced,
After the lithium aluminium hydride reduction tetrahydrofuran solution is added dropwise to complete, continue to stir 25-35min,
The 3-sec-butyl lithium borohydride mixed solution is filtered by the filter of 800 mesh, obtains water white transparency
3-sec-butyl lithium borohydride tetrahydrofuran solution,
The 3-sec-butyl lithium borohydride tetrahydrofuran solution is distilled, obtains the three sec-butyl boron that concentration is 1mol/L
Lithium hydride tetrahydrofuran solution.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114394987A (en) * | 2022-01-27 | 2022-04-26 | 沧州临港星辰化工有限公司 | Preparation method of trialkyl lithium borohydride |
| CN114920764A (en) * | 2022-04-08 | 2022-08-19 | 安徽泽升科技有限公司 | Preparation method of lithium tri-sec-butyl borohydride and application of lithium tri-sec-butyl borohydride in preparation of antibacterial agent |
-
2016
- 2016-05-31 CN CN201610379585.1A patent/CN107446003A/en active Pending
Non-Patent Citations (5)
| Title |
|---|
| HERBERT C. BROWN等: ""Organoboranes. 43. A Convenient, Highly Efficient Synthesis of Triorganylboranes via a Modified Organometallic Route"", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| HERBERT C. BROWN等: ""Rapid Reaction of Trialkylboranes with Lithium Aluminum Hydride in the Presence of Triethylenediamine. Facile and Quantitative Synthesis of Lithium Trialkylborohydrides Including Derivatives with Exceptionally Large Steric Requirements"", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| HERBERT C. BROWN等: ""ULTRASONICS IN ORGANOBORANE CHEMISTRY. RAPID SYNTHESIS OF TRIORGANYLBORANES VIA A MODIFIED ORGANOMETALLIC ROUTE"", 《TETRAHEDRON LETTERS》 * |
| 车荣睿: ""三乙基硼氢化锂在有机合成中的应用"", 《精细化工》 * |
| 车荣睿: ""碱金属烷基硼氢化物合成和应用的进展"", 《化学通报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114394987A (en) * | 2022-01-27 | 2022-04-26 | 沧州临港星辰化工有限公司 | Preparation method of trialkyl lithium borohydride |
| CN114394987B (en) * | 2022-01-27 | 2022-08-05 | 沧州临港星辰化工有限公司 | Preparation method of trialkyl lithium borohydride |
| CN114920764A (en) * | 2022-04-08 | 2022-08-19 | 安徽泽升科技有限公司 | Preparation method of lithium tri-sec-butyl borohydride and application of lithium tri-sec-butyl borohydride in preparation of antibacterial agent |
| CN115894540A (en) * | 2022-04-08 | 2023-04-04 | 安徽泽升科技有限公司 | Preparation method of lithium tri-sec-butyl borohydride |
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