CN107011372A - A kind of method for preparing lithium hexamethyldisilazide - Google Patents
A kind of method for preparing lithium hexamethyldisilazide Download PDFInfo
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- CN107011372A CN107011372A CN201710338349.XA CN201710338349A CN107011372A CN 107011372 A CN107011372 A CN 107011372A CN 201710338349 A CN201710338349 A CN 201710338349A CN 107011372 A CN107011372 A CN 107011372A
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- China
- Prior art keywords
- reactor
- lithium hexamethyldisilazide
- solution
- head tank
- preparing lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 14
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims abstract description 33
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical class C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052786 argon Inorganic materials 0.000 claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical compound [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 claims description 3
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims description 3
- 230000035935 pregnancy Effects 0.000 claims description 2
- 238000005070 sampling Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910017435 S2 In Inorganic materials 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000004888 barrier function Effects 0.000 abstract description 2
- 238000010792 warming Methods 0.000 description 8
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- DCERHCFNWRGHLK-UHFFFAOYSA-N C[Si](C)C Chemical compound C[Si](C)C DCERHCFNWRGHLK-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- VGTCWWMCIQYNFC-UHFFFAOYSA-N acetylene;lithium Chemical compound [Li].C#C VGTCWWMCIQYNFC-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- -1 enol lithium salts Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000005051 trimethylchlorosilane 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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention discloses a kind of method for preparing lithium hexamethyldisilazide, comprise the following steps：S1, chooses 500L reactor, is dried after reactor is cleaned, it is ensured that the inside clean dried of reactor, and check pressure gauge, thermometer and bottom valve；S2, with argon gas replacement reaction kettle 36 times；S3,170 190kg tetrahydrofurans, 90 110kg HMDSs are sequentially added by head tank to reactor；S4, by reactor internal cooling in the range of 40 DEG C 35 DEG C, keep this temperature, open balance pipe valve, by head tank be added dropwise quality be 171kg, the n-butyllithium solution that molar concentration is 1.6M 2.5M, dripped off in 2 7h, then heat to 10 DEG C, it is incubated 1h, you can obtain lithium hexamethyldisilazide solution.The present invention overcomes conventional lithium hexamethyldisilazide can not obtain the technology barrier of high concentration product, by adjusting reaction ratio and temperature control, successfully completes the lithium hexamethyldisilazide of various concentrations, the synthesis yield of product is more than 90%.
Description
Technical field
The present invention relates to technical field of chemistry and chemical engineering, more particularly to a kind of method for preparing lithium hexamethyldisilazide.
Background technology
Lithium hexamethyldisilazide (LiHMDS) can be used for the metal complex for preparing low ligancy, because part
(TMS)2N- steric hindrance is very big.Such example has M [N (TMS)2]3（M=Sc,Ti,V,Fe；TMS=(CH3)3Si)）.With trimethyl
Chlorosilane reaction produces three (trimethyl silicon substrate) amine, and the wherein ligancy of nitrogen is 3, and steric configuration is plane regular triangle.Having
In machine synthesis or pharmaceutical synthesis, lithium hexamethyldisilazide is typically used as highly basic, and various lithium salts examples are formed by exchange reaction
Acetylene lithium is such as formed, or prepares enol lithium salts etc. and further completes functional group's conversion.
Prior art can not obtain high concentration product when preparing lithium hexamethyldisilazide, cause low production efficiency,
For this, we have proposed a kind of method for preparing lithium hexamethyldisilazide.
The content of the invention
The technical problem existed based on background technology, the present invention proposes a kind of side for preparing lithium hexamethyldisilazide
Method.
A kind of method for preparing lithium hexamethyldisilazide proposed by the present invention, comprises the following steps：
S1, chooses 500L reactor, is dried after reactor is cleaned, it is ensured that the inside clean dried of reactor, and examine
Look into pressure gauge, thermometer and bottom valve；
S2, with argon gas replacement reaction kettle 3-6 times；
S3,170-190kg tetrahydrofurans, 90-110kg HMDSs are sequentially added by head tank to reactor；
S4, in the range of extremely -40 DEG C -35 DEG C of reactor internal cooling, keeps this temperature, opens balance pipe valve, passes through a high position
It is the n-butyllithium solution that 166-176kg, molar concentration are 1.6M-2.5M that quality, which is added dropwise, in groove, drips off, then heats up in 2-7h
To 10 DEG C, 1h is incubated, you can obtain lithium hexamethyldisilazide solution, chemical equation is as follows,
（Me3Si）2NH+BuLi®（Me3Si）2Nli+BuH；
S5, to lithium hexamethyldisilazide solution sampling and detectable concentration.
Preferably, in the S2, with argon gas replacement reaction kettle 3 times.
Preferably, in the S3,180kg tetrahydrofurans, 100kg hexamethyls two are sequentially added to reactor by head tank
Silazane.
Preferably, in the S4, by reactor internal cooling to -10 DEG C, this temperature is kept, balance pipe valve is opened, passes through
It is the n-butyllithium solution that 171kg, molar concentration are 1.6M-2.5M that quality, which is added dropwise, in head tank, drips off, then heats in 6h
10 DEG C, it is incubated 1h, you can obtain lithium hexamethyldisilazide solution.
Preferably, the n-BuLi is the hexane solution of n-BuLi.
Preferably, the molar concentration of the lithium hexamethyldisilazide solution is 1.0M-1.6M.
In the present invention, lithium hexamethyldisilazide is dissolved in organic solvent by HMDS, low temperature
Lower instillation n-butyllithium solution reacts to form lithium hexamethyldisilazide solution with HMDS, resulting pregnancy
The silicon substrate lithium amide solution of base two contains lithium hexamethyldisilazide, organic solvent-normal hexane, tetrahydrofuran.The present invention overcome with
The technology barrier of high concentration product can not be obtained toward lithium hexamethyldisilazide, by adjusting reaction ratio and temperature control,
The lithium hexamethyldisilazide of various concentrations is successfully completed, the synthesis yield of product is more than 90%.
Embodiment
The present invention is made with reference to specific embodiment further to explain.
Embodiment 1
Ensure 500L reactors, be clean dried, before the deadline, bottom valve is turned off for pressure gauge, thermometer, is replaced with argon gas
Reactor three times；180kg tetrahydrofurans are added to reactor by head tank, 100kg HMDSs are cooled to -15
DEG C ± 5 DEG C, this temperature is kept, balance pipe valve is opened, it is that 171kg, molar concentration are 1.6M-2.5M that quality, which is added dropwise, by head tank
N-butyllithium solution（2.5M hexane solution）, about 6h drips off, and is warming up to 10 DEG C, is incubated 1h, obtains the silicon substrate amino of hexamethyl two
Lithium solution, samples detectable concentration, yield 98%.
Embodiment 2
Ensure 500L reactors, be clean dried, before the deadline, bottom valve is turned off for pressure gauge, thermometer, is replaced with argon gas
Reactor three times；180kg tetrahydrofurans are added to reactor by head tank, 100kg HMDSs are cooled to -20
DEG C ± 5 DEG C, this temperature is kept, balance pipe valve is opened, it is that 171kg, molar concentration are 1.6M-2.5M that quality, which is added dropwise, by head tank
N-butyllithium solution（2.5M hexane solution）, about 6h drips off, and is warming up to 10 DEG C, is incubated 1h, obtains the silicon substrate amino of hexamethyl two
Lithium solution, samples detectable concentration, yield 97%.
Embodiment 3
Ensure 500L reactors, be clean dried, before the deadline, bottom valve is turned off for pressure gauge, thermometer, is replaced with argon gas
Reactor three times；180kg tetrahydrofurans are added to reactor by head tank, 100kg HMDSs are cooled to -10
DEG C ± 5 DEG C, this temperature is kept, balance pipe valve is opened, it is that 171kg, molar concentration are 1.6M-2.5M that quality, which is added dropwise, by head tank
N-butyllithium solution（2.5M hexane solution）, about 2h drips off, and is warming up to 10 DEG C, is incubated 1h, obtains the silicon substrate amino of hexamethyl two
Lithium solution, samples detectable concentration, yield 96%.
Embodiment 4
Ensure 500L reactors, be clean dried, before the deadline, bottom valve is turned off for pressure gauge, thermometer, is replaced with argon gas
Reactor three times；180kg tetrahydrofurans are added to reactor by head tank, 100kg HMDSs are cooled to 0 DEG C
± 5 DEG C, keep this temperature, open balance pipe valve, it is that 171kg, molar concentration are 1.6M-2.5M's that quality, which is added dropwise, by head tank
N-butyllithium solution（2.5M hexane solution）, about 6h drips off, and is warming up to 10 DEG C, is incubated 1h, obtains lithium hexamethyldisilazide
Solution, samples detectable concentration, yield 94%.
Embodiment 5
Ensure 500L reactors, be clean dried, before the deadline, bottom valve is turned off for pressure gauge, thermometer, is replaced with argon gas
Reactor 4 times；170kg tetrahydrofurans are added to reactor by head tank, 90kg HMDSs are cooled to 5 DEG C ± 5
DEG C, keep this temperature, open balance pipe valve, by head tank be added dropwise quality be 171kg, molar concentration be 1.6M-2.5M just
Butyl lithium solution（2.5M hexane solution）, about 3h drips off, and is warming up to 10 DEG C, is incubated 1h, obtains lithium hexamethyldisilazide molten
Liquid, samples detectable concentration, yield 93%.
Embodiment 5
Ensure 500L reactors, be clean dried, before the deadline, bottom valve is turned off for pressure gauge, thermometer, is replaced with argon gas
Reactor 4 times；By head tank to reactor add 175kg tetrahydrofurans, 95kg HMDSs, be cooled to 10 DEG C ±
5 DEG C, keep this temperature, open balance pipe valve, by head tank be added dropwise quality be 168kg, molar concentration be 1.6M-2.5M just
Butyl lithium solution（2.5M hexane solution）, about 4h drips off, and is warming up to 10 DEG C, is incubated 1h, obtains lithium hexamethyldisilazide molten
Liquid, samples detectable concentration, yield 92%.
Embodiment 6
Ensure 500L reactors, be clean dried, before the deadline, bottom valve is turned off for pressure gauge, thermometer, is replaced with argon gas
Reactor 5 times；178kg tetrahydrofurans are added to reactor by head tank, 100kg HMDSs are cooled to 15 DEG C
± 5 DEG C, keep this temperature, open balance pipe valve, it is that 171kg, molar concentration are 1.6M-2.5M's that quality, which is added dropwise, by head tank
N-butyllithium solution（2.5M hexane solution）, about 5h drips off, and is warming up to 10 DEG C, is incubated 1h, obtains lithium hexamethyldisilazide
Solution, samples detectable concentration, yield 91%.
Embodiment 7
Ensure 500L reactors, be clean dried, before the deadline, bottom valve is turned off for pressure gauge, thermometer, is replaced with argon gas
Reactor 6 times；180kg tetrahydrofurans are added to reactor by head tank, 105kg HMDSs are cooled to 10 DEG C
± 5 DEG C, keep this temperature, open balance pipe valve, it is that 172kg, molar concentration are 1.6M-2.5M's that quality, which is added dropwise, by head tank
N-butyllithium solution（2.5M hexane solution）, about 6h drips off, and is warming up to 10 DEG C, is incubated 1h, obtains lithium hexamethyldisilazide
Solution, samples detectable concentration, yield 90%.
The foregoing is only a preferred embodiment of the present invention, but protection scope of the present invention be not limited thereto,
Any one skilled in the art the invention discloses technical scope in, technique according to the invention scheme and its
Inventive concept is subject to equivalent substitution or change, should all be included within the scope of the present invention.
Claims (6)
1. a kind of method for preparing lithium hexamethyldisilazide, it is characterised in that comprise the following steps：
S1, chooses 500L reactor, is dried after reactor is cleaned, it is ensured that the inside clean dried of reactor, and examine
Look into pressure gauge, thermometer and bottom valve；
S2, with argon gas replacement reaction kettle 3-6 times；
S3,170-190kg tetrahydrofurans, 90-110kg HMDSs are sequentially added by head tank to reactor；
S4, in the range of extremely -40 DEG C -35 DEG C of reactor internal cooling, keeps this temperature, opens balance pipe valve, passes through a high position
It is the n-butyllithium solution that 166-176kg, molar concentration are 1.6M-2.5M that quality, which is added dropwise, in groove, drips off, then heats up in 2-7h
To 10 DEG C, 1h is incubated, you can obtain lithium hexamethyldisilazide solution, chemical equation is as follows,
(Me3Si)2NH+BuLi®(Me3Si)2Nli+BuH；
S5, to lithium hexamethyldisilazide solution sampling and detectable concentration.
2. a kind of method for preparing lithium hexamethyldisilazide according to claim 1, it is characterised in that the S2
In, with argon gas replacement reaction kettle 3 times.
3. a kind of method for preparing lithium hexamethyldisilazide according to claim 1, it is characterised in that the S3
In, 180kg tetrahydrofurans, 100kg HMDSs are sequentially added to reactor by head tank.
4. a kind of method for preparing lithium hexamethyldisilazide according to claim 1, it is characterised in that the S4
In, by reactor internal cooling to -10 DEG C, keep this temperature, open balance pipe valve, by head tank be added dropwise quality be 171kg,
Molar concentration is 1.6M-2.5M n-butyllithium solution, is dripped off in 6h, then heats to 10 DEG C, is incubated 1h, you can obtain six
The silicon substrate lithium amide solution of methyl two.
5. a kind of method for preparing lithium hexamethyldisilazide according to claim 1, it is characterised in that the positive fourth
Base lithium is the hexane solution of n-BuLi.
6. a kind of method for preparing lithium hexamethyldisilazide according to claim 1, it is characterised in that the pregnancy
The molar concentration of the silicon substrate lithium amide solution of base two is 1.0M-1.6M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710338349.XA CN107011372A (en) | 2017-05-15 | 2017-05-15 | A kind of method for preparing lithium hexamethyldisilazide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710338349.XA CN107011372A (en) | 2017-05-15 | 2017-05-15 | A kind of method for preparing lithium hexamethyldisilazide |
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| CN107011372A true CN107011372A (en) | 2017-08-04 |
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| CN201710338349.XA Pending CN107011372A (en) | 2017-05-15 | 2017-05-15 | A kind of method for preparing lithium hexamethyldisilazide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707929A (en) * | 2020-12-24 | 2021-04-27 | 绍兴上虞华伦化工有限公司 | Process for preparing bis (trimethyl disilyl) lithium amide |
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| US20030220267A1 (en) * | 2001-08-16 | 2003-11-27 | Matteson Donald S. | Borinic acid protease inhibitors |
| CN101792469A (en) * | 2010-03-05 | 2010-08-04 | 南京航空航天大学 | Ultrasonic assisted method for synthesizing lanthanum tris[bis(trimethylsilyl)amide] |
| KR20130095582A (en) * | 2012-02-20 | 2013-08-28 | 연세대학교 산학협력단 | Triazole group substituted porphyrin derivative and method for preparing the same |
| CN103965248A (en) * | 2014-05-26 | 2014-08-06 | 中北大学 | Compound bis-spirophosphoryl nitrogen silane and preparation method thereof |
| CN104387415A (en) * | 2014-11-25 | 2015-03-04 | 浙江硕而博化工有限公司 | Method for preparing hexamethyl-disilane amine lithium solution and reaction device thereof |
-
2017
- 2017-05-15 CN CN201710338349.XA patent/CN107011372A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030220267A1 (en) * | 2001-08-16 | 2003-11-27 | Matteson Donald S. | Borinic acid protease inhibitors |
| CN101792469A (en) * | 2010-03-05 | 2010-08-04 | 南京航空航天大学 | Ultrasonic assisted method for synthesizing lanthanum tris[bis(trimethylsilyl)amide] |
| KR20130095582A (en) * | 2012-02-20 | 2013-08-28 | 연세대학교 산학협력단 | Triazole group substituted porphyrin derivative and method for preparing the same |
| CN103965248A (en) * | 2014-05-26 | 2014-08-06 | 中北大学 | Compound bis-spirophosphoryl nitrogen silane and preparation method thereof |
| CN104387415A (en) * | 2014-11-25 | 2015-03-04 | 浙江硕而博化工有限公司 | Method for preparing hexamethyl-disilane amine lithium solution and reaction device thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112707929A (en) * | 2020-12-24 | 2021-04-27 | 绍兴上虞华伦化工有限公司 | Process for preparing bis (trimethyl disilyl) lithium amide |
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