CN106397288B - The preparation method of biphenyls liquid crystal material - Google Patents
The preparation method of biphenyls liquid crystal material Download PDFInfo
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- CN106397288B CN106397288B CN201510460228.3A CN201510460228A CN106397288B CN 106397288 B CN106397288 B CN 106397288B CN 201510460228 A CN201510460228 A CN 201510460228A CN 106397288 B CN106397288 B CN 106397288B
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Abstract
The present invention provides a kind of preparation method of biphenyls liquid crystal material, the biphenyls liquid crystal material is shown in formula IThe preparation of the biphenyls liquid crystal material includes the following steps: 1) to synthesize: in the first organic solvent, by the compound of Formula IIThe compound of formula IIIAnd alkali, suzuki reaction occurs for heating under the effect of the catalyst:Wherein, R1For-F or-NH2, R2For the alkyl with 3-7 carbon atom, the unsaturated alkyl with 3-7 carbon atom or the alkoxy with 3-7 carbon atom, L1, L2, L3And L4Respectively H or F, m 0,1 or 2, X be-Cl ,-Br or-I,ForOr
Description
Technical field
The present invention relates to liquid crystal material fields, in particular to a kind of preparation method of biphenyls liquid crystal material.
Background technique
Stereoscopic display is the developing direction of display field, and especially naked eye 3D display is not necessarily to wearing spectacles, it will is 3D aobvious
The main trend shown.
In bore hole 3D display device, a kind of device of light splitting is needed accurately to pass Pixel Information distinguishing in display
It is sent to the images of left and right eyes of people, common light-splitting device has lens, slit etc..Lens can be broadly divided into two kinds, saturating one is having
The physical form of mirror routine, such as curved-surface structure are often used polymerizable anisotropic optical material and pass through UV polymerization or hot polymerization
The methods of conjunction preparation, but be not suitable for scale of mass production, and yield is lower；Another kind is liquid crystal lens, and liquid crystal material is clipped in
Among two layers of electrode base board, using the electrical response characteristics of liquid crystal material, applies the optical property that voltage changes liquid crystal layer, pass through electricity
Field gradient acts on the effect that lens can be achieved, and the production line of available liquid crystal display screen can be used to be given birth in liquid crystal lens
It produces, is conducive to scale of mass production and popularization.
Commonly used high birefringence rate liquid crystal material is generally the small-molecule mixture for having specific structure, figure in liquid crystal lens
1 is the common molecular structure of high birefringence rate liquid crystal material, two band side chain (R1) or end group (R2) ring structure (A1, A2) by
Linking group (X) connects.
Fig. 2 is a kind of common biphenyl class molecular structure in high birefringence rate liquid crystal material, chemical structure to temperature and
Ultraviolet light etc. is relatively stable, and it has significant effect to the birefringence and clearing point that promote liquid crystal material.Therefore wide
It is general applied in liquid crystal material and the one type of liquid crystal material of most study.
Synthesis for the biphenyls liquid crystal molecular structure of Fig. 2, generally using suzuki reaction, (Suzuki is anti-in the prior art
Answer) such monomer liquid crystal is prepared, as shown in Figure 3.
Suzuki reaction has some irreplaceable advantages, if reaction yield is higher, condition in the preparation of this class formation
It is relatively mild, reaction step is simple etc..But there are also inevitable disadvantages for suzuki reaction, such as catalyst metals palladium
It is not easy to remove, remaining Metal Palladium will significantly reduce the resistivity of liquid crystal material, and influence its sound in display device
Answer voltage；For another example reaction substrate boric acid can generate the by-product of itself coupling under suzuki reaction condition, purify post-processing
Become complicated.Especially preparing cyano (CN) and when different sulphur itrile group (NCS) class liquid crystal monomer, due to itself coupling by-product with
The polarity of final product CN, NCS class liquid crystal monomer is very close, when itself coupling product and final product mix, uses
Column chromatography chromatogram method is difficult to separate them, causes final product purifying to become complicated, therefore preparing final reacting product CN,
Before NCS class liquid crystal monomer step, it is necessary to itself coupling by-product be removed, guarantee the purity of final product.
Currently, the common purification process for suzuki post-processing is column chromatography chromatogram method, that is, utilize product and by-product
Opposed polarity product and by-product are separated, to reach purifying purpose, but because prepared by column chromatography chromatogram method
When amount becomes larger, the time of required cost, disengaging time and eluting solvent are greatly increased, and corresponding column chromatographs pillar
Also it to increase, be highly detrimental to industrialized mass production.
Therefore a simple and effective method need to be provided to prepare biphenyls liquid crystal material, simplifies purification of products method, and
And guarantee that yield and purity are higher, it is convenient for mass production.
Summary of the invention
In order to simplify the method for purification of biphenyls liquid crystal material, the present invention proposes a kind of preparation side of biphenyls liquid crystal material
Method, the biphenyls liquid crystal material are shown in formula I:
The preparation of the biphenyls liquid crystal material includes the following steps:
1) it synthesizes: in the first organic solvent, by the compound of Formula IIThe compound of formula IIIAnd alkali,
Suzuki reaction occurs for heating under the effect of the catalyst:
Wherein, R1For-F or-NH2, R2For the alkyl with 3-7 carbon atom, the unsaturated hydrocarbons with 3-7 carbon atom
Base or alkoxy with 3-7 carbon atom, L1, L2, L3And L4Respectively H or F, m 0,1 or 2, X be-Cl ,-Br or-I,For
2) purify: it is above-mentioned after the reaction was completed, step 1) reaction product is purified with cable type extractor according.
Further, the step 2) the purification the following steps are included:
A. the reaction solution is poured into ice water, stir and hydrochloric acid is added dropwise to neutrality, keep the alkali in the reaction solution complete
It has reacted in portion；
B. the resulting liquid of step a is extracted with the second organic solvent, collects organic phase, first washed with salt described organic
Phase then dries the organic phase with anhydrous sodium sulfate, finally, rotary evaporation, which does the organic phase, obtains brown solid；
C. petroleum ether is added in the extraction flask of Soxhlet extractor, the resulting brown solid of step b is added in extraction tube,
After being heated to reflux 1~2 hour, the petroleum ether of extraction flask is cooled to room temperature, product solid is precipitated, and is filtered using Suction filtration device
To purified product.
Further, second organic solvent is selected from one of methylene chloride, ethyl acetate and ether.
Further, the reaction of the step 1) carries out in an inert atmosphere.
Further, in the step 1), first solvent is selected from ethyl alcohol, isopropanol, Isosorbide-5-Nitrae-dioxane, N, N- bis-
One of methylformamide and toluene.
6 is further, and in the step 1), the alkali is selected from Cs2CO3、K2CO3、Na2CO3、Li2CO3、K3PO4And Ba
(OH)2One of.
Further, in the step 1), the catalyst is palladium catalyst.
Further, the catalyst includes Pd (Pph3)4,Pb(dppf)Cl2With Pd (Pph3)2Cl2One of.
Further, the reaction time of the step 1) is 2~5 hours.
Further, the preparation method further comprises step 3): in third organic solvent, being added obtained by step 2)
Purified product and CSCl2, the purified product and CSCl of the step 2)2Following reaction occurs:
Wherein, R1For-NH2, R2For the alkyl with 3-7 carbon atom, the unsaturated alkyl with 3-7 carbon atom or
Alkoxy with 3-7 carbon atom, L1, L2, L3And L4Respectively H or F, m 0,1 or 2,For
Further, the third organic solvent is selected from one of chloroform and methylene chloride.
Further, the preparation method further comprises step 3): the resulting purified product of step 2) and nitrous is added
Acid sodium aqueous solution, and the nickel potassium cyanide for being dissolved in ammonia and ammonium chloride buffer solution is added dropwise to reaction solution, the purification of the step 2) produces
Object reacts as follows with the generation of nickel potassium cyanide:
Wherein, R1For-NH2, R2For the alkyl with 3-7 carbon atom, the unsaturated alkyl with 3-7 carbon atom or
Alkoxy with 3-7 carbon atom, L1, L2, L3And L4Respectively H or F, m 0,1 or 2,For
Further, the preparation method specifically includes:
A: the resulting purified product of step 2) and dilute hydrochloric acid are added in reaction flask, and reaction is placed in ice bath, slowly
Sodium nitrite in aqueous solution is added dropwise, is reacted 1~4 hour under condition of ice bath；
B: it is above-mentioned after the reaction was completed, above-mentioned reaction solution is adjusted to neutrality with sodium carbonate dissolution, and be dissolved in reaction solution dropwise addition
The nickel potassium cyanide of ammonia and ammonium chloride buffer solution, then rises to 60 DEG C for reaction.
Detailed description of the invention
Fig. 1 is the common molecular structure of high birefringence rate liquid crystal material.
Fig. 2 is high birefringence rate liquid crystal material biphenyl class molecular structure.
The suzuki synthetic method of Fig. 3 biphenyl class molecule.
Fig. 4 is that embodiment 1 utilizes soxhlet extraction purified product procedure chart.
Specific embodiment
To better understand the objects, features and advantages of the present invention, with reference to the accompanying drawing and specific real
Applying mode, the present invention is further described in detail.It should be noted that in the absence of conflict, the implementation of the application
Feature in example and embodiment can be combined with each other.
In the following description, numerous specific details are set forth in order to facilitate a full understanding of the present invention, still, the present invention may be used also
To be implemented using other than the one described here other modes, therefore, the present invention is not limited to following public specific realities
Apply the limitation of example.
Embodiment 1
The present embodiment isPreparation:
Step 1) synthesizes target product:
Back flow reaction device is built, stirrer is put into reaction flask, 4- pentylbiphenyl boric acid, the fluoro- 4- of 2,6- bis- is added
Bromaniline, catalyst Pd (Pph3)4, cesium carbonate；Sealed reaction system, by the air displacement in sealing system at nitrogen；Injection
There are n,N-Dimethylformamide and water, stir and be slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.After 4 hours, use
TLC detects the extent of reaction.
Step 2) is purified with product of the cable type extractor according to step 1):
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 1-2 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid
It is precipitated, is filtered using Suction filtration device, obtain 98% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
The present invention carries out purification process using product crude product of the cable type extractor according to step 1), and product crude product includes mesh
Mark product, itself coupling by-product and other by-products.Due to product, itself coupling by-product and other by-products are in petroleum
Different dissolubilities in ether, dissolubility are as follows: itself coupling by-product (readily soluble) > product (being partly dissolved) > other by-products are (difficult
It is molten), and Metal Palladium indissoluble in petroleum ether.
As shown in figure 4, being heated to reflux with petroleum ether, since itself coupling by-product is soluble in petroleum ether, first
Extraction flask is flowed into petroleum ether；Partly soluble target product increases also with the number of extracting, all by extracting to mentioning
Bottle is taken, and other by-products (metal palladium catalyst etc.) for being insoluble in petroleum ether then stay in extraction tube.
To be extracted to finish, cooling extraction flask, in cooling procedure, target product is slowly precipitated from petroleum ether, at this time only
It needs to filter, collects filter admittedly, can be obtained purer product, if desired more pure products, recrystallize again.
Step 3) prepares final product:
Back flow reaction device is built, is put into stirrer into reaction flask, above-mentioned steps 2 are added) product after purification and molten
Agent methylene chloride or chloroform, stirring and dissolving, and reaction flask is placed in ice bath, CSCl is slowly added dropwise in ice bath temperature to be cooled to2,
It is added dropwise, removes ice bath, after reaction solution is slowly warmed to room temperature, start to be heated to reflux reaction.After 12 hours, examined with TLC
Survey the extent of reaction；After completion of the reaction, sodium carbonate liquor is added, makes excessive CSCl2It runs out of, organic phase is then demultiplex out, institute
It is then dry with anhydrous sodium sulfate or anhydrous magnesium sulfate after obtaining organic phase salt washing twice, finally, rotary evaporation does organic phase
Brown-red oil is obtained, may separate out the final product that purity is 99% or more using column chromatography chromatogram method.
In addition, purification of the step 2) to product, purifies the NCS class final product (or CN class final product) of step 3)
Compare crucial.Itself the coupling by-product and the final product polarity of step 3) generated due to step 1) reaction process is connect very much
Closely, with column chromatography chromatogram method purify final product when, if not to itself be coupled by-product advanced processing, itself coupling by-product with
Final product is difficult to separate, it is necessary to pass through separating for several times, this necessarily causes, and yield reduces or even part-structure is through separating for several times
It can not separate completely, cause purity that can not be promoted.Therefore itself coupling by-product must be removed in advance, utilize the above Soxhlet extraction
Method can dexterously solve the shadow that itself coupling by-product purifies CN class or NCS class biphenyl liquid crystal monomer final product
It rings.
The preparation method of biphenyls liquid crystal material provided by the invention, easy to operate, apparatus is simple, and a Xu Suoshi is mentioned
It takes device and uses Suction filtration device；Solvent is saved, using Soxhlet extractor, is only needed compared to column chromatography chromatogram method less molten
Extracting can be completed in agent；Purification loss is few, and yield is higher than the yield of column chromatography chromatogram method general 80% or more；The production of acquisition
Object purity is high, generally 97% or more；Due to instrument, step is simple, and required solvent is few, expends the advantages such as the time is few, therefore, this
Method has feasibility in industrialized mass production.
Embodiment 2
The present embodiment isPreparation:
Step 1) synthesizes target product:
Back flow reaction device is built, stirrer is put into reaction flask, is added2,6-
Two fluoro- 4- chloroanilines, catalyst Pb (dppf) Cl2And potassium carbonate；Sealed reaction system, by the air displacement in sealing system
At nitrogen；It is injected with Isosorbide-5-Nitrae-dioxane and water, stir and is slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.5 is small
Shi Hou detects the extent of reaction with TLC.
Step 2) is purified with product of the cable type extractor according to step 1):
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 2 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 98% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
Step 3) prepares final product:
Back flow reaction device is built, is put into stirrer into reaction flask, above-mentioned steps 2 are added) product after purification and molten
Agent methylene chloride or chloroform, stirring and dissolving, and reaction flask is placed in ice bath, CSCl is slowly added dropwise in ice bath temperature to be cooled to2,
It is added dropwise, removes ice bath, after reaction solution is slowly warmed to room temperature, start to be heated to reflux reaction.After 12 hours, examined with TLC
Survey the extent of reaction；After completion of the reaction, sodium carbonate liquor is added, makes excessive CSCl2It runs out of, organic phase is then demultiplex out, institute
It is then dry with anhydrous sodium sulfate or anhydrous magnesium sulfate after obtaining organic phase salt washing twice, finally, rotary evaporation does organic phase
Brown-red oil is obtained, may separate out the final product that purity is 99% or more using column chromatography chromatogram method.
Embodiment 3
The present embodiment isPreparation:
Step 1) prepares final product:
Back flow reaction device is built, stirrer is put into reaction flask, 4- propyl phenyl boric acid, 4- Iodoaniline, catalysis is added
Agent Pd (Pph3)2Cl2, sodium carbonate；Sealed reaction system, by the air displacement in sealing system at nitrogen；Be injected with isopropanol and
Water is stirred and is slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.After 2 hours, the extent of reaction is detected with TLC.
Step 2) is purified with product of the cable type extractor according to step 1):
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 2 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 99% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
The preparation method of biphenyls liquid crystal material provided by the invention, easy to operate, apparatus is simple, and a Xu Suoshi is mentioned
It takes device and uses Suction filtration device；Solvent is saved, using Soxhlet extractor, is only needed compared to column chromatography chromatogram method less molten
Extracting can be completed in agent；Purification loss is few, and yield is higher than the yield of column chromatography chromatogram method general 80% or more；The production of acquisition
Object purity is high, generally 97% or more；Due to instrument, step is simple, and required solvent is few, expends the advantages such as the time is few, therefore, this
Method has feasibility in industrialized mass production.
Embodiment 4
The present embodiment isPreparation:
Step 1) prepares target product:
Back flow reaction device is built, stirrer is put into reaction flask, 4- (trans- -4- pentylcyclohexyl) benzene boron is added
Acid, the fluoro- 4- bromaniline of 2,6- bis-, catalyst Pb (dppf) Cl2With Ba (OH)2；Sealed reaction system, by the sky in sealing system
Gas is replaced as nitrogen；It is injected with isopropyl alcohol and water, stir and is slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.4 is small
Shi Hou detects the extent of reaction with TLC.
Step 2) purifies step 1) crude product with cable type extractor according:
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 2 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 97% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
Step 3) prepares final product:
Back flow reaction device is built, is put into stirrer into reaction flask, above-mentioned steps 2 are added) product after purification and molten
Agent methylene chloride or chloroform, stirring and dissolving, and reaction flask is placed in ice bath, CSCl is slowly added dropwise in ice bath temperature to be cooled to2,
It is added dropwise, removes ice bath, after reaction solution is slowly warmed to room temperature, start to be heated to reflux reaction.After 12 hours, examined with TLC
Survey the extent of reaction；After completion of the reaction, sodium carbonate liquor is added, makes excessive CSCl2It runs out of, organic phase is then demultiplex out, institute
It is then dry with anhydrous sodium sulfate or anhydrous magnesium sulfate after obtaining organic phase salt washing twice, finally, rotary evaporation does organic phase
Brown-red oil is obtained, may separate out the final product that purity is 99% or more using column chromatography chromatogram method.
Embodiment 5
The present embodiment isPreparation:
Step 1) prepares target product:
Back flow reaction device is built, stirrer is put into reaction flask, is added2,6-
Two fluoro- 4- bromanilines, catalyst Pd (Pph3)4And K3PO4；Sealed reaction system, by the air displacement in sealing system at nitrogen
Gas；It is injected with toluene and water, stir and is slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.After 4 hours, examined with TLC
Survey the extent of reaction.
Step 2) purifies step 1) crude product with cable type extractor according:
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 2 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 98% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
Step 3) prepares final product:
It is put into stirrer in reaction flask, above-mentioned steps 2 is added) product and dilute hydrochloric acid after purification, and reaction is placed in ice
In bath, sodium nitrite in aqueous solution is slowly added dropwise；Under condition of ice bath after reaction 2 as a child, dissolved with sodium carbonate by above-mentioned reaction
Liquid is adjusted to neutrality, and the nickel potassium cyanide for being dissolved in ammonia and ammonium chloride buffer solution is added dropwise to reaction solution, and reaction is then risen to 60 DEG C,
Reaction 15 minutes carries out suction filtration and solid, the collection filtrate with a small amount of washing filter to reaction solution, is extracted to filtrate through row with methylene chloride
It takes, collects organic phase, it is then dry with anhydrous magnesium sulfate after gained organic phase is washed twice with salt, finally, rotary evaporation is dry to be had
Machine mutually obtains faint yellow solid, may separate out the final product that purity is 99% or more using column chromatography chromatogram method.
Embodiment 6
The present embodiment isPreparation:
Step 1) prepares target product:
Back flow reaction device is built, stirrer is put into reaction flask, 4- propyl boric acid benzene, the fluoro- 4- bromine of 2,6- bis- is added
Aniline, catalyst Pd (Pph3)2Cl2, sodium carbonate；Sealed reaction system, by the air displacement in sealing system at nitrogen；Injection
There is isopropyl alcohol and water, stir and be slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.After 2.5 hours, detected with TLC
The extent of reaction.
Step 2) purifies step 1) crude product with cable type extractor according:
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 3 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 98% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
Step 3) prepares final product:
It is put into stirrer in reaction flask, above-mentioned steps 2 is added) product and dilute hydrochloric acid after purification, and reaction is placed in ice
In bath, sodium nitrite in aqueous solution is slowly added dropwise；Under condition of ice bath after reaction 2 as a child, dissolved with sodium carbonate by above-mentioned reaction
Liquid is adjusted to neutrality, and the nickel potassium cyanide for being dissolved in ammonia and ammonium chloride buffer solution is added dropwise to reaction solution, and reaction is then risen to 60 DEG C,
Reaction 15 minutes carries out suction filtration and solid, the collection filtrate with a small amount of washing filter to reaction solution, is extracted to filtrate through row with methylene chloride
It takes, collects organic phase, it is then dry with anhydrous magnesium sulfate after gained organic phase is washed twice with salt, finally, rotary evaporation is dry to be had
Machine mutually obtains faint yellow solid, may separate out the final product that purity is 99% or more using column chromatography chromatogram method.
Embodiment 7
The present embodiment isPreparation:
Step 1) prepares target product:
Back flow reaction device is built, stirrer is put into reaction flask, 4- propoxyl group hexamethylene ylboronic acid, 2,6- bis- is added
Fluoro- 4- bromaniline, catalyst Pd (Pph3)2Cl2, sodium carbonate；Sealed reaction system, by the air displacement in sealing system at nitrogen
Gas；It is injected with isopropyl alcohol and water, stir and is slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.After 3 hours, TLC is used
Detect the extent of reaction.
Step 2) purifies step 1) crude product with cable type extractor according:
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 1 hour, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 98% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
Step 3) prepares final product:
It is put into stirrer in reaction flask, above-mentioned steps 2 is added) product and dilute hydrochloric acid after purification, and reaction is placed in ice
In bath, sodium nitrite in aqueous solution is slowly added dropwise；Under condition of ice bath after reaction 2 as a child, dissolved with sodium carbonate by above-mentioned reaction
Liquid is adjusted to neutrality, and the nickel potassium cyanide for being dissolved in ammonia and ammonium chloride buffer solution is added dropwise to reaction solution, and reaction is then risen to 60 DEG C,
Reaction 15 minutes carries out suction filtration and solid, the collection filtrate with a small amount of washing filter to reaction solution, is extracted to filtrate through row with methylene chloride
It takes, collects organic phase, it is then dry with anhydrous magnesium sulfate after gained organic phase is washed twice with salt, finally, rotary evaporation is dry to be had
Machine mutually obtains faint yellow solid, may separate out the final product that purity is 99% or more using column chromatography chromatogram method.
Embodiment 8
The present embodiment isPreparation:
Step 1) prepares final product:
Back flow reaction device is built, stirrer is put into reaction flask, is addedThe fluoro- 4- of 1-
Bromobenzene, catalyst Pd (Pph3)4And sodium carbonate；Sealed reaction system, by the air displacement in sealing system at nitrogen；It is injected with
Isopropyl alcohol and water is stirred and is slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.After 5 hours, is detected and reacted with TLC
Degree.
Step 2) purifies step 1) crude product with cable type extractor according:
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 2 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 97% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
The preparation method of biphenyls liquid crystal material provided by the invention, easy to operate, apparatus is simple, and a Xu Suoshi is mentioned
It takes device and uses Suction filtration device；Solvent is saved, using Soxhlet extractor, is only needed compared to column chromatography chromatogram method less molten
Extracting can be completed in agent；Purification loss is few, and yield is higher than the yield of column chromatography chromatogram method general 80% or more；The production of acquisition
Object purity is high, generally 97% or more；Due to instrument, step is simple, and required solvent is few, expends the advantages such as the time is few, therefore, this
Method has feasibility in industrialized mass production.
Embodiment 9
The present embodiment isPreparation:
Step 1) prepares final product:
Back flow reaction device is built, stirrer is put into reaction flask, 4- pentylbiphenyl boric acid, the fluoro- 4- of 1,2- bis- is added
Bromobenzene, catalyst Pd (Pph3)2Cl2, sodium carbonate；Sealed reaction system, by the air displacement in sealing system at nitrogen；Injection
There is isopropyl alcohol and water, stir and be slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.After 5 hours, detected with TLC anti-
Answer degree.
Step 2) purifies step 1) crude product with cable type extractor according:
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 2 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 97% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
Embodiment 10
The present embodiment isPreparation:
Step 1) prepares final product:
Back flow reaction device is built, stirrer is put into reaction flask, 4- pentylbiphenyl boric acid, the fluoro- 4- of 1,2- bis- is added
Bromobenzene, catalyst Pd (Pph3)4, sodium carbonate；Sealed reaction system, by the air displacement in sealing system at nitrogen；It is injected with different
Third alcohol and water is stirred and is slowly heated to reflux, it is ensured that system is reacted under nitrogen protection.After 5 hours, reaction interval is detected with TLC
Degree.
Step 2) purifies step 1) crude product with cable type extractor according:
After completion of the reaction, reaction solution is poured into ice water, dilute hydrochloric acid is added dropwise and stirred, dropped to neutrality, make the carbon in reaction solution
Sour sodium total overall reaction is complete；Aforesaid liquid is extracted with dichloromethane, collects organic phase and is connect after gained organic phase is washed twice with salt
It is dry with anhydrous sodium sulfate or anhydrous magnesium sulfate, finally, rotary evaporation, which does organic phase, obtains brown solid, brown solid is at this time
The crude product of suzuki reaction includes target product, itself coupling by-product and other by-products.Extraction element is put up,
Petroleum ether is poured into the extraction flask of Soxhlet extractor；By above-mentioned brown solid loaded on inside filtration paper cylinder, filtration paper cylinder is placed on
The extraction tube of Soxhlet extractor；It is heated to reflux 2 hours, the petroleum ether of extraction flask is cooled to room temperature or lower, product solid analysis
Out, it is filtered using Suction filtration device, obtains 97% or more product of purity.
Soxhlet extraction and column chromatography chromatogram method compare:
The above is only a preferred embodiment of the present invention, is not intended to restrict the invention, for those skilled in the art
For member, the invention may be variously modified and varied.All within the spirits and principles of the present invention, it is made it is any modification,
Equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (8)
1. a kind of method for preparing biphenyls liquid crystal material and preparing isothiocyano class liquid crystal monomer with it, the biphenyl class liquid
Brilliant material is shown in formula I:
Include the following steps:
1) it synthesizes: in the first organic solvent, by the compound of Formula IIThe compound of formula IIIAnd alkali,
Suzuki reaction occurs for heating under the action of catalyst:
Wherein, R1For-F or-NH2, R2For the alkyl with 3-7 carbon atom, the unsaturated alkyl with 3-7 carbon atom or
Alkoxy with 3-7 carbon atom, L1, L2, L3And L4Respectively H or F, m 0,1 or 2, X be-Cl ,-Br or-I,For
2) purify: it is above-mentioned after the reaction was completed, purified with cable type extractor according to step 1) reaction product: a. is by the reaction solution
Ice water is poured into, stir and hydrochloric acid is added dropwise to neutrality, keeps the alkali total overall reaction in the reaction solution complete；B. organic molten with second
Agent extracts the resulting liquid of step a, collects organic phase, first washes the organic phase with salt, then dry with anhydrous sodium sulfate
The dry organic phase, finally, rotary evaporation, which does the organic phase, obtains brown solid；Second organic solvent is selected from dichloromethane
One of alkane, ethyl acetate and ether；C. petroleum ether is added in the extraction flask of Soxhlet extractor, the step is added in extraction tube
The resulting brown solid of rapid b, after being heated to reflux 1~2 hour, the petroleum ether of extraction flask is cooled to room temperature, and product solid is precipitated,
Purified product is obtained by filtration using Suction filtration device；
3) in third organic solvent, the resulting purified product of step 2) and CSCl is added2, the purified product of the step 2) with
CSCl2Following reaction occurs:
Wherein, R1For-NH2, R2For the alkyl with 3-7 carbon atom, the unsaturated alkyl with 3-7 carbon atom or have
The alkoxy of 3-7 carbon atom, L1, L2, L3And L4Respectively F, m 0,1 or 2,For
After completion of the reaction, sodium carbonate liquor is added, makes excessive CSCl2It runs out of.
2. preparation method according to claim 1, which is characterized in that the reaction of the step 1) in an inert atmosphere into
Row.
3. preparation method according to claim 1, which is characterized in that in the step 1), first solvent is selected from second
One of alcohol, isopropanol, 1,4- dioxane, N,N-dimethylformamide and toluene.
4. preparation method according to claim 1, which is characterized in that in the step 1), the alkali is selected from Cs2CO3、
K2CO3、Na2CO3、Li2CO3、K3PO4With Ba (OH)2One of.
5. preparation method according to claim 1, which is characterized in that in the step 1), the catalyst is palladium chtalyst
Agent.
6. preparation method according to claim 5, which is characterized in that the catalyst includes Pd (Pph3)4,Pb(dppf)
Cl2With Pd (Pph3)2Cl2One of.
7. preparation method according to claim 1, which is characterized in that the reaction time of the step 1) is 2~5 hours.
8. preparation method according to claim 1, which is characterized in that the third organic solvent is selected from chloroform and dichloromethane
One of alkane.
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