CN107739388A - A kind of preparation method of phenyl lithium - Google Patents
A kind of preparation method of phenyl lithium Download PDFInfo
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- CN107739388A CN107739388A CN201711084523.9A CN201711084523A CN107739388A CN 107739388 A CN107739388 A CN 107739388A CN 201711084523 A CN201711084523 A CN 201711084523A CN 107739388 A CN107739388 A CN 107739388A
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- sodium
- lithium
- preparation
- bromobenzene
- phenyl lithium
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- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims abstract description 90
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 229910000733 Li alloy Inorganic materials 0.000 claims abstract description 50
- 239000001989 lithium alloy Substances 0.000 claims abstract description 50
- VVNXEADCOVSAER-UHFFFAOYSA-N lithium sodium Chemical compound [Li].[Na] VVNXEADCOVSAER-UHFFFAOYSA-N 0.000 claims abstract description 50
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 238000009413 insulation Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 42
- 229910052786 argon Inorganic materials 0.000 claims description 21
- 239000007789 gas Substances 0.000 claims description 21
- 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 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- 239000011734 sodium Substances 0.000 claims description 14
- 239000004480 active ingredient Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- CPWPJLJWUXOOAB-UHFFFAOYSA-N benzene;bromine Chemical compound [Br].C1=CC=CC=C1 CPWPJLJWUXOOAB-UHFFFAOYSA-N 0.000 claims 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- WPUJEWVVTKLMQI-UHFFFAOYSA-N benzene;ethoxyethane Chemical compound CCOCC.C1=CC=CC=C1 WPUJEWVVTKLMQI-UHFFFAOYSA-N 0.000 abstract description 4
- 230000001960 triggered effect Effects 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 16
- 239000000047 product Substances 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 12
- 150000002900 organolithium compounds Chemical class 0.000 description 11
- 230000000977 initiatory effect Effects 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 230000008859 change Effects 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 239000003507 refrigerant Substances 0.000 description 7
- 239000004305 biphenyl Substances 0.000 description 6
- 235000010290 biphenyl Nutrition 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 4
- 229910052794 bromium Inorganic materials 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 230000031709 bromination Effects 0.000 description 3
- 238000005893 bromination reaction Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002902 organometallic compounds Chemical class 0.000 description 2
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001502 aryl halides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UBAZGMLMVVQSCD-UHFFFAOYSA-N carbon dioxide;molecular oxygen Chemical compound O=O.O=C=O UBAZGMLMVVQSCD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010959 commercial synthesis reaction Methods 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002901 organomagnesium compounds Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent 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
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/02—Lithium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation method of phenyl lithium, comprise the following steps：(1) under inert gas shielding, sodium lithium alloy and n-butyl ether are added into system, stirs to obtain sodium lithium alloy dispersion liquid；(2) at 10~30 DEG C, bromobenzene is added dropwise in the sodium lithium alloy dispersion liquid obtained under stirring to step (1), rear insulation reaction is added dropwise through handling to obtain phenyl lithium solution at 10~30 DEG C in control system temperature.The present invention substitutes conventional ether or ether benzene mixed liquor using n-butyl ether, and by strict controlling reaction temperature, reaction is successfully triggered, and product purity is higher, realizes the production of the industrially scalable of phenyl lithium.
Description
Technical field
The invention belongs to organo-metallic compound to synthesize field, and in particular to a kind of preparation method of phenyl lithium.
Background technology
Organo-lithium compound is a kind of important organo-metallic compound, and just being used early in nineteen twenty-nine by K.Ziegler has
Machine halide is prepared with lithium metal reaction, and is then applied in organic synthesis.At present, organo-lithium compound conduct
A kind of important synthetic agent, plays an important role in fundamental research and commercial synthesis.Ziegler has found organolithium
Compound has similar property and application value in organic synthesis to organo-magnesium compound (Grignard reagents), and
Some aspects compared with Grignard reagents, have reactivity is stronger, yield is high, reduction inclination is smaller, product can be easily separated,
The features such as a variety of non-polar solvens can be dissolved in, so as to replace Grignard reagents in organic synthesis or make up
Deficiency of the Grignard reagents in some synthesis.Meanwhile organo-lithium compound has unique property in some organic syntheses
Can so that it is with a wide range of applications and important meaning in organic synthesis.
The preparation of organo-lithium compound mainly has following approach：
(1) halogenated hydrocarbons acts on lithium metal
With alkyl or aryl halide, in appropriate non-polar solven (hexamethylene, pentane, ether, petroleum ether etc.), with
Lithium metal directly acts on, you can obtains organo-lithium compound.
(2) addition of alkene and lithium metal
With the addition of lithium metal and alkene carbon-carbon double bond, organo-lithium compound can be made.Especially when carbon-carbon double bond and virtue
Base or unsaturated bond are easier that addition occurs in the case of being in conjugation, obtain organo-lithium compound.
(3) exchange reaction between compound
Prepared by the exchange reaction of metal-metal；Prepared by the exchange reaction of metal-halogen；Exchange by hydrogen-metal is anti-
It should prepare., generally can be with the exchange reaction between compound come to prepare some organo-lithium compounds be very important approach
Prepare the organo-lithium compound that first two method is not easy directly to produce.
Phenyl lithium is conventional organo-lithium compound, in the prior art typically by bromobenzene or chlorobenzene and lithium metal in ether or
React and be made in ether-benzene mixed liquor, or acted on by mercury diphenide and lithium metal and obtained in toluene, this method is present due to benzene
Base lithium is excessively active, and raw material is relatively more stable, and when commercial scale is amplified to, reaction is often difficult to trigger, success rate
It is relatively low, it cannot get target product.Because the dosage of phenyl lithium in basic research and industrial production is huge and has irreplaceability,
The problem of how to realize the large-scale production of phenyl lithium turns into a urgent need to resolve.
The content of the invention
The invention provides a kind of preparation method of phenyl lithium, the yield for the phenyl lithium that the preparation method obtains is high, especially
It is suitable for plant-scale production of phenyl lithium.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of phenyl lithium, comprises the following steps：
(1) under inert gas shielding, sodium-lithium alloy and n-butyl ether are added into system, stir sodium-lithium alloy disperses
Liquid；
(2) at 10~30 DEG C, bromobenzene, control volume is added dropwise in the sodium-lithium alloy dispersion liquid obtained under stirring to step (1)
Be temperature at 10~30 DEG C, rear insulation reaction is added dropwise through handling to obtain phenyl lithium solution.
In the prior art, there is boiling point as dispersant, such dispersant usually using ether or ether-benzene mixed liquor
The shortcomings that low, easy system poison, security difference, the present invention replaces ether or ether-benzene mixed liquor to be kept away as dispersant using n-butyl ether
Exempt from using low boiling, low-flash, easily make malicious solvent, there is the advantages of boiling point height is not volatile, and reaction yield is higher.
Preferably, the mass fraction of sodium is 1~6% in described sodium-lithium alloy, and the present invention uses to be replaced in sodium-lithium alloy
Substituting metal lithium, the initiation of reaction can be promoted.
Further preferably, the mass fraction of sodium is 1~3% in described sodium-lithium alloy, increases sodium in sodium-lithium alloy
Mass fraction, the initiation of reaction is may advantageously facilitate, but sodium content is too high, can make the content of impurity in product increase.
In step (1), the mass ratio that adds of sodium-lithium alloy and n-butyl ether is 1：10~30.
Requirement of the course of reaction of sodium-lithium alloy and bromobenzene to moisture, air (such as oxygen, carbon dioxide) is higher,
Before production, enter line replacement to the air in whole production system with inert gas, described inert gas is argon gas, argon gas it is close
Degree is higher than air, and anhydrous and oxygen-free condition is easily controllable, and described inert gas is using preceding needing by drying process.
The reaction of bromobenzene and sodium-lithium alloy is generally difficult to trigger, and success rate is relatively low, and very sensitive to temperature, less than 10
Just stop reaction after DEG C, once even if reacting stopping heating and bromobenzene being added dropwise can not all save.Simultaneously temperature not above 30 DEG C,
Not so coupled product can largely be produced.
Preferably, in step (2), bromobenzene is dissolved in after n-butyl ether in instillation system again, obtained bromobenzene n-butyl ether solution
Mass percent concentration be 40~60%.
Preferably, as active ingredients, the dosage of bromobenzene is sodium-lithium alloy quality in system in bromobenzene n-butyl ether solution
10~20 times.
Preferably, in step (2), bromobenzene is added dropwise in 6~8h, and the purity of product and the rate of addition of bromobenzene are close
Correlation, rate of addition is too fast to produce coupled product.
Preferably, the dropwise addition process of bromobenzene will monitor the concentration of product phenyl lithium in real time, and production concentration stops when not increasing
Bromobenzene is added dropwise.
In step (2), bromobenzene is incubated after being added dropwise continues reaction 1~2 hour.
In step (2), described processing includes：Under argon gas protective condition, settled, filtered and washed with n-butyl ether
Wash and dilute.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) by adjusting the mass fraction of the sodium in sodium-lithium alloy, the reaction of generation phenyl lithium is enable smoothly to trigger
And progress；
(2) by the temperature of strict control system and the rate of addition of bromobenzene, containing for impurity in product has been efficiently controlled
Amount, ensure that the quality of product.
Embodiment
Further detailed description is done to the present invention with reference to specific embodiment.
Embodiment 1
By the 500L reactors of clean dried with argon gas replace 3 times it is stand-by, argon gas protection under, to 500L reactors put into
48.42kg n-butyl ethers, 3.9kg sodium-lithium alloy (mass fraction of sodium is 3% in sodium-lithium alloy), stir to obtain sodium-lithium alloy point
Dispersion liquid；
Control reactor temperature that 88kg is slowly added dropwise into sodium-lithium alloy dispersion liquid under stirring between 10~30 DEG C
Concentration is 45wt% bromobenzene n-butyl ether solution initiation reaction, and reaction is initiated (reaction solution change milkiness) immediately, after reaction triggers
Temperature is drastically raised, and refrigerant cooling, whole strict control system temperature is reacted between 10~30 DEG C, and about 6~8h is added dropwise
Finish, the dropwise addition process of bromobenzene will monitor the concentration of product phenyl lithium in real time, and production concentration must stop that bromine is added dropwise when not increasing
Benzene.After dripping bromobenzene, insulation reaction 1h, it is cooled to and is stored at room temperature, is filtered with sand plate funnel, reactor and much filtrate (bromination
Lithium solid) washed with n-butyl ether, obtain concentration be 1.5M phenyl lithium solution, yield 80%, wherein, the matter of accessory substance biphenyl
It is 0.2% to measure degree.
The concentration for the phenyl lithium solution that the present invention obtains is measured by the method for acid base titration of the prior art.
Embodiment 2
By the 500L reactors of clean dried with argon gas replace 3 times it is stand-by, argon gas protection under, to 500L reactors put into
60kg n-butyl ethers, 5.88kg sodium-lithium alloy (in sodium-lithium alloy the mass fraction of sodium be 1%), stir sodium-lithium alloy disperses
Liquid；
Control reactor temperature that 120kg is slowly added dropwise into sodium-lithium alloy dispersion liquid under stirring between 10~30 DEG C
Concentration is 50wt% bromobenzene n-butyl ether solution initiation reaction, and reaction is initiated (reaction solution change milkiness) immediately, after reaction triggers
Temperature is drastically raised, and refrigerant cooling, whole strict control system temperature is reacted between 10~30 DEG C, and about 6~8h is added dropwise
Finish, the dropwise addition process of bromobenzene will monitor the concentration of product phenyl lithium in real time, and production concentration must stop that bromine is added dropwise when not increasing
Benzene.After dripping bromobenzene, insulation reaction 1.5h, it is cooled to and is stored at room temperature, is filtered with sand plate funnel, reactor and much filtrate (bromine
Change lithium solid) washed with n-butyl ether, obtain the phenyl lithium solution that concentration is 1.9M, yield 78%, wherein, accessory substance biphenyl
Mass percentage content is 0.8%.
Embodiment 3
By the 500L reactors of clean dried with argon gas replace 3 times it is stand-by, argon gas protection under, to 500L reactors put into
44.25kg n-butyl ethers, 2.89kg sodium-lithium alloy (mass fraction of sodium is 6% in sodium-lithium alloy), stir to obtain sodium-lithium alloy point
Dispersion liquid；
Reactor temperature is controlled to be slowly added dropwise between 10~30 DEG C under stirring into sodium-lithium alloy dispersion liquid
73.75kg concentration is 40wt% bromobenzene n-butyl ether solution initiation reaction, and reaction is initiated (reaction solution change milkiness) immediately, is reacted
Temperature is drastically raised after initiation, and refrigerant cooling, whole strict control system temperature is reacted between 10~30 DEG C, about 6~
8h is added dropwise, and the dropwise addition process of bromobenzene will monitor the concentration of product phenyl lithium in real time, and production concentration must stop when not increasing
Bromobenzene is added dropwise.After dripping bromobenzene, insulation reaction 1.5h, it is cooled to and is stored at room temperature, is filtered, reactor and filtered out with sand plate funnel
Thing (lithium bromide solid) is washed with n-butyl ether, obtain concentration be 1.1M phenyl lithium solution, yield 70%, wherein, accessory substance
The mass percentage content of biphenyl is 1.2%.
Comparative example 1
By the 500L reactors of clean dried with argon gas replace 3 times it is stand-by, argon gas protection under, to 500L reactors put into
48.42kg n-butyl ethers, 3.9kg lithium grains, stir lithium dispersion liquid；
Control reactor temperature is slowly added dropwise 88kg concentration into the dispersion liquid of lithium between 10~30 DEG C, under stirring and is
45wt% bromobenzene n-butyl ether solution, it is found that reaction can not trigger, reaction failure.
Comparative example 2
By the 500L reactors of clean dried with argon gas replace 3 times it is stand-by, argon gas protection under, to 500L reactors put into
48.42kg n-butyl ethers, 3.9kg sodium-lithium alloy (mass fraction of sodium is 12% in sodium-lithium alloy), stir to obtain sodium-lithium alloy point
Dispersion liquid；
Control reactor temperature that 88kg is slowly added dropwise into sodium-lithium alloy dispersion liquid under stirring between 10~30 DEG C
Concentration is 45wt% bromobenzene n-butyl ether solution initiation reaction, and reaction is initiated (reaction solution change milkiness) immediately, after reaction triggers
Temperature is drastically raised, and refrigerant cooling, whole strict control system temperature is reacted between 10~30 DEG C, and about 6~8h is added dropwise
Finish, the dropwise addition process of bromobenzene will monitor the concentration of product phenyl lithium in real time, and production concentration must stop that bromine is added dropwise when not increasing
Benzene.After dripping bromobenzene, insulation reaction 1h, it is cooled to and is stored at room temperature, is filtered with sand plate funnel, reactor and much filtrate (bromination
Lithium solid) washed with n-butyl ether, obtain concentration be 0.8M phenyl lithium solution, yield 79%, wherein, accessory substance biphenyl is detected
Go out, mass percentage content 0.7%.
Comparative example 3
By the 500L reactors of clean dried with argon gas replace 3 times it is stand-by, argon gas protection under, to 500L reactors put into
48.42kg n-butyl ethers, 3.9kg sodium-lithium alloy (mass fraction of sodium is 3% in sodium-lithium alloy), stir to obtain sodium-lithium alloy point
Dispersion liquid；
Control reactor temperature that 88kg is slowly added dropwise into sodium-lithium alloy dispersion liquid under stirring between 10~30 DEG C
Concentration is 45wt% bromobenzene n-butyl ether solution initiation reaction, and reaction is initiated (reaction solution change milkiness) immediately, after reaction triggers
Temperature drastically raises, and refrigerant cooling, course of reaction temperature control causes system temperature to be less than 10 DEG C, and reaction stops immediately, even if
Heating and dropwise addition bromobenzene can not all be saved, and production concentration does not increase all the time, reaction failure.
Comparative example 4
By the 500L reactors of clean dried with argon gas replace 3 times it is stand-by, argon gas protection under, to 500L reactors put into
48.42kg n-butyl ethers, 3.9kg sodium-lithium alloy (mass fraction of sodium is 3% in sodium-lithium alloy), stir to obtain sodium-lithium alloy point
Dispersion liquid；
Control reactor temperature that 88kg is slowly added dropwise into sodium-lithium alloy dispersion liquid under stirring between 10~30 DEG C
Concentration is 45wt% bromobenzene n-butyl ether solution initiation reaction, and reaction is initiated (reaction solution change milkiness) immediately, after reaction triggers
Temperature drastically raises, and refrigerant cooling, course of reaction temperature control causes system temperature to be higher than 30 DEG C, continues that bromobenzene n-butyl ether is added dropwise
Solution, about 6~8h are added dropwise, and the dropwise addition process of bromobenzene will monitor the concentration of product phenyl lithium in real time, and production concentration does not increase
Shi Bixu stops that bromobenzene is added dropwise.After dripping bromobenzene, insulation reaction 1h, it is cooled to and is stored at room temperature, is filtered with sand plate funnel, reaction
Kettle and much filtrate (lithium bromide solid) are washed with n-butyl ether, obtain concentration be 0.8M phenyl lithium solution, yield 65%, its
In, accessory substance biphenyl is detected, mass percentage content 2.4%.
Comparative example 5
By the 500L reactors of clean dried with argon gas replace 3 times it is stand-by, argon gas protection under, to 500L reactors put into
48.42kg n-butyl ethers, 3.9kg sodium-lithium alloy (mass fraction of sodium is 3% in sodium-lithium alloy), stir to obtain sodium-lithium alloy point
Dispersion liquid；
Control reactor temperature that 88kg is slowly added dropwise into sodium-lithium alloy dispersion liquid under stirring between 10~30 DEG C
Concentration is 45wt% bromobenzene n-butyl ether solution initiation reaction, and reaction is initiated (reaction solution change milkiness) immediately, after reaction triggers
Temperature is drastically raised, and refrigerant cooling, whole strict control system temperature is reacted between 10~30 DEG C, and about 3-5h is dripped
Finish.After dripping bromobenzene, insulation reaction 1h, it is cooled to and is stored at room temperature, is filtered with sand plate funnel, reactor and much filtrate (bromination
Lithium solid) washed with n-butyl ether, obtain concentration be 0.5M phenyl lithium solution, yield 60%, wherein, accessory substance biphenyl is detected
Go out, mass percentage content 5.2%.
Claims (10)
1. a kind of preparation method of phenyl lithium, it is characterised in that comprise the following steps：
(1) under inert gas shielding, sodium-lithium alloy and n-butyl ether are added into system, stirs to obtain sodium-lithium alloy dispersion liquid；
(2) at 10~30 DEG C, bromobenzene, control system temperature is added dropwise in the sodium-lithium alloy dispersion liquid obtained under stirring to step (1)
Rear insulation reaction is added dropwise through handling to obtain phenyl lithium solution at 10~30 DEG C in degree.
2. the preparation method of phenyl lithium according to claim 1, it is characterised in that the matter of sodium in described sodium-lithium alloy
It is 1~6% to measure fraction.
3. the preparation method of phenyl lithium according to claim 2, it is characterised in that the matter of sodium in described sodium-lithium alloy
It is 1~3% to measure fraction.
4. the preparation method of phenyl lithium according to claim 1, it is characterised in that in step (1), sodium-lithium alloy and just
Butyl ether adds mass ratio as 1：10~30.
5. the preparation method of phenyl lithium according to claim 1, it is characterised in that described inert gas is argon gas.
6. the preparation method of phenyl lithium according to claim 1, it is characterised in that in step (2), bromobenzene is in 6~8h
It is added dropwise.
7. the preparation method of the phenyl lithium according to any one of claim 1 or 6, it is characterised in that in step (2), by bromine
Benzene is dissolved in after n-butyl ether in instillation system again, and the mass percent concentration of obtained bromobenzene n-butyl ether solution is 40~60%.
8. the preparation method of phenyl lithium according to claim 7, it is characterised in that as active ingredients, bromobenzene n-butyl ether
The dosage of bromobenzene is 10~20 times of sodium-lithium alloy quality in system in solution.
9. the preparation method of phenyl lithium according to claim 1, it is characterised in that in step (2), after bromobenzene is added dropwise
Insulation continues reaction 1~2 hour.
10. the preparation method of phenyl lithium according to claim 1, it is characterised in that in step (2), described processing bag
Include：Under argon gas protective condition, settled, filter and washed and diluted with n-butyl ether.
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| CN (1) | CN107739388A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992019622A1 (en) * | 1991-04-29 | 1992-11-12 | Fmc Corporation | Aryllithium process |
| CN103044461A (en) * | 2013-01-16 | 2013-04-17 | 上虞华伦化工有限公司 | Preparation method of tert-butyllithium solution |
-
2017
- 2017-11-07 CN CN201711084523.9A patent/CN107739388A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1992019622A1 (en) * | 1991-04-29 | 1992-11-12 | Fmc Corporation | Aryllithium process |
| CN103044461A (en) * | 2013-01-16 | 2013-04-17 | 上虞华伦化工有限公司 | Preparation method of tert-butyllithium solution |
Non-Patent Citations (2)
| Title |
|---|
| 夏道宏 等主编: "《有机化学实验》", 30 September 2007, 中国石油大学出版社 * |
| 王积涛 等编著: "《金属有机化学》", 31 October 1989, 高等教育出版社 * |
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