CN109082280A - A kind of preparation method of liquid crystal material - Google Patents
A kind of preparation method of liquid crystal material Download PDFInfo
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- CN109082280A CN109082280A CN201811305638.0A CN201811305638A CN109082280A CN 109082280 A CN109082280 A CN 109082280A CN 201811305638 A CN201811305638 A CN 201811305638A CN 109082280 A CN109082280 A CN 109082280A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K19/126—Compounds containing at least one asymmetric carbon atom
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/10—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings
- C09K19/12—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing at least two benzene rings at least two benzene rings directly linked, e.g. biphenyls
- C09K2019/128—Compounds containing phenylene-1,2-diyl
Abstract
The invention discloses a kind of preparation methods of liquid crystal material; belong to liquid crystal material technical field; raw material o ethyl aniline and salicylaldhyde used in the present invention are cheap and easy to get; wherein, o ethyl aniline obtains intermediate biphenyl boric acid by halogen, lithiumation boration in the upper bromine of acetyl group protection, Suzuki coupling, deprotection diazotising；Meanwhile salicylaldhyde through upper bromine, Williamson etherification reaction, Wittig reaction, hydroboration-oxidation react to obtain intermediate bromobenzene containing alcohol ether, biphenylboronic acid and bromobenzene containing alcohol ether through Suzuki coupling, at ester, be deprotected and obtain final liquid crystal material.The solvent that the present invention uses more environmental protection, easy controlled operation, risk factor is less, and Suzuki coupling reaction does not generate the coupling impurity that polysubstituted halides generate, and one-step reaction selectivity is high.The present invention uses convergence type highway route design, and total recovery is up to 40% or more, and cost is relatively low, better economic benefit.
Description
Technical field
The invention belongs to liquid crystal material technical fields, are related to a kind of preparation method of liquid crystal material.
Background technique
With the development of science and technology, various electronical display products are widely used in life, and liquid crystal display panel is liquid crystal
The important component of display (Liquid Crystal Display, LCD), usually by two display panels and display surface
Liquid crystal layer composition between plate, liquid crystal molecule reverses under field plate effect, by controlling the incident light polarization across liquid crystal layer
To show that image, common liquid crystal display panel have TN (Twisted Nematic, twisted nematic) liquid crystal display panel, IPS (In-
Plane Switching, plane conversion type) liquid crystal display panel and VA (Vertical Alignment, vertical orientation type) liquid crystal
Panel.
TN liquid crystal display panel is widely used in the liquid crystal display of entry level and low and middle-end, since it exports gray scale levels
Number is less, and liquid crystal molecule deflection speed is fast, causes its response time to be easy to improve, the Pros and Cons of TN liquid crystal display panel are very bright
Aobvious, cheap, the response time is its advantage place fastly, but the undesirable and brought color of visible angle is not as good as IPS liquid crystal
Panel and VA liquid crystal display panel are its apparent disadvantages.
IPS liquid crystal display panel has visible angle height, the accurate advantage of color rendition, its electrode arrangements are not upper and lower two
End, but on the both sides of bottom glass, improve visual angle in such a way that liquid crystal molecule plane switches, using space thickness, rubs
The change that intensity simultaneously efficiently uses transverse electric field driving is wiped, liquid crystal molecule is allowed to do maximum Plane Rotation angle to increase visual angle,
The shortcomings that this design is that panel aperture ratio (light penetration) is low, often needs more backlights.
VA liquid crystal display panel is present advanced liquid crystal using more panel type, and 16.7M color and big visible angle are these
The characteristics of class panel, under VA mode, liquid crystal molecule under the action of vertical orientation power perpendicular to glass panel, when applying certain electricity
Liquid crystal molecule starts turning after pressure, exports picture, and the advantages of VA liquid crystal display panel is that positive (facing) contrast highest, text are shown
Effect is clearly sharp keen, black white contrast is high, the disadvantage is that the uniformity of screen is inadequate, color drift often occurs.
Merck & Co., Inc. reports in patent US20150252265A1 (hereinafter referred to as comparative example 1) with vertical orientation knot
The liquid crystal material of structure, goal of the invention are simplified display apparatus manufacturing methods, while the advantages of possessing VA-IPS technology is (good
View angle dependency, shorter response time and high contrast), the structural formula and preparation process of liquid crystal material are as follows:
The route is tandem highway route design, and first step coupling reaction has bromine coupling impurity, product choosing in reaction process
Selecting property is poor, and comprehensive yied is low, and only 3.5%.
Zhejiang discloses very much a kind of liquid crystal Jie in number of patent application 201710137712.1 (hereinafter referred to as comparative example 2) forever
The synthetic method of matter, preparation route are as follows:
Preparation process through Suzuki coupling, is deprotected, anti-at ether, Wittig using Multi substituted benzenes boric acid as starting material
Answer, hydroboration-oxidation, at ester, deprotection and etc. obtain liquid crystal material, first step coupling reaction equally has bromine in the route
It is coupled impurity, product yield is caused to reduce, simultaneous reactions are using the higher Multi substituted benzenes boric acid of price as raw material, by a series of anti-
Step is answered just to obtain liquid crystal material, preparation cost is high, is unfavorable for large-scale production.
Comprehensive analysis, in the case where high quality panel demand constantly increases, polymerizable vertical orientation liquid crystal media conduct
A kind of important potential liquid crystal material has wide application space, develops a high income, low cost, easy-operating synthesis
Route is necessary.
Summary of the invention
The present invention in order to overcome the drawbacks of the prior art, devises a kind of preparation method of liquid crystal material, Suzuki coupling
Reaction does not generate the coupling impurity that polysubstituted halides generate, and one-step reaction selectivity is high, and total recovery is up to 40% or more,
Compared with the route high income of patent report, cost is relatively low, better economic benefit.
Specific technical solution adopted by the present invention is: a kind of preparation method of liquid crystal material, it is critical that by following step
It is rapid to carry out:
(1) using o ethyl aniline shown in formula I as starting material, upper bromine is protected to obtain acetylamino shown in formula II through acetyl group
Bromobenzene；
(2) acetylamino bromobenzene shown in formula II is coupled to obtain acetylamino biphenyl shown in formula III through a step Suzuki；
(3) acetylamino biphenyl shown in formula III obtains biphenyl halides shown in formula IV through halogen in deprotection, diazotising；
(4) biphenyl halides shown in formula IV react to obtain biphenyl boron shown in formula V with boron alkyl acid esters through n-BuLi lithiumation
Acid；
(5) it using salicylaldhyde shown in formula VI as raw material, is obtained shown in formula VII through upper bromine, Williamson etherification reaction
Ether-containing bromobenzene；
(6) ether-containing bromobenzene shown in formula VII successively passes through Wittig reaction, hydroboration-oxidation reacts to obtain alcohol-containing shown in formula VIII
Ether bromobenzene；
(7) biphenylboronic acid shown in bromobenzene containing alcohol ether and formula V shown in formula VIII obtains Ⅸ institute of formula through a step Suzuki coupling reaction
Show terphenyl ethyl alcohol；
(8) terphenyl ethyl alcohol and methacrylic chloride shown in formula Ⅸ obtain terphenyl acrylate shown in formula Ⅹ at ester；
(9) terphenyl acrylate shown in formula Ⅹ obtains final product liquid crystal material shown in formula Ⅺ through deprotection；
The structural formula of above-mentioned various shown compound is as follows:
Wherein, R is one of bromine Br or iodine I；
R1Selected from one of having structure group:
Step (1) is that o ethyl aniline shown in formula I is dissolved in solvent A, is added acetic anhydride at -5~20 DEG C, TLC with
Track to reaction terminates, and reaction solution is cooled to -5~20 DEG C, and bromine and hydrogen peroxide is added, and reacts 2~8h, TLC, which is tracked to, to have reacted
Finish, aqueous solution of sodium bisulfite is added, reaction solution obtains acetylamino bromobenzene shown in formula II through liquid separation, washing, concentration.
Step (2) be acetylamino bromobenzene shown in the formula II that obtains step (1) with to amyl phenyl boric acid in alkaline condition
Under in solvent B after room temperature deaerates stir 0.5~2h, palladium-containing catalyst is then added, then be placed in 60~120 DEG C reaction 2~
8h, TLC track to end of reaction, and reaction solution is washed, is concentrated, and obtain acetylamino biphenyl shown in formula III.
Step (3) is that acetylamino biphenyl shown in formula III that step (2) obtains is dissolved in solvent C, be added 20wt%~
60wt% aqueous sulfuric acid is heated to reflux 0.5~4h, stops heating and being cooled to -20~0 DEG C, sodium nitrite in aqueous solution is added dropwise；
Again to cuprous bromide is added in another there-necked flask, hydrobromic acid aqueous solution forms cuprous bromide-hydrobromic acid solution, at 20~60 DEG C
Diazonium salt is added drop-wise in cuprous bromide-hydrobromic acid solution, 2~8h is reacted, TLC tracks to end of reaction, reaction solution through extraction,
Washing, dry, concentration, obtain biphenyl bromine shown in formula IV；
Either, step (3) is that acetylamino biphenyl shown in formula III that step (2) obtains is dissolved in solvent C, is added
10wt%~30wt% aqueous hydrochloric acid solution or 20wt%~60wt% aqueous sulfuric acid are heated to reflux 0.5~4h, stop heating simultaneously
It is cooled to -20~0 DEG C, sodium nitrite in aqueous solution is added dropwise；Potassium iodide aqueous solution is added to another there-necked flask again, -20~30
Diazonium salt is added drop-wise in potassium iodide aqueous solution at DEG C, reacts 2~8h, TLC tracks to end of reaction, and reaction solution is through extraction, water
It washes, dry, be concentrated, obtain biphenyl iodine shown in formula IV.
Step (4) is that biphenyl halides shown in formula IV that step (3) obtains are dissolved in solvent D, through inert gas shielding
0.5~2h is stirred, -40~-80 DEG C of dropwise addition lithium hexane solutions are cooled to, after stirring 0.5~2h, instills alkylboronic acids
Ester, then be placed in -20~-80 DEG C of reactions 2~4h, TLC and track to end of reaction, addition aqueous hydrochloric acid solution hydrolysis at -20~30 DEG C,
Reaction solution obtains biphenylboronic acid shown in formula V through liquid separation, washing, concentration.
Step (5) is that salicylaldhyde shown in formula VI is dissolved in solvent E, and bromine is added dropwise at -20~30 DEG C, reaction
2~8h, TLC track to end of reaction, and sodium sulfite is then added and stirs 0.5~2h, after liquid separation, washing, drying, are added
Solvent F dissolution, is then added organic bromide R1- Br and alkali, through inert gas shielding, in 80~120 DEG C of return stirrings 2~
8h, TLC, which track to reaction, to be terminated, reaction solution through liquid separation, washing, drying, be concentrated to get ether-containing bromobenzene shown in formula VII, wherein R1For
One of following groups:
Step (6) be ether-containing bromobenzene shown in the formula VII that obtains step (5) and methyl Wittig reagent under alkaline condition,
In solvent G under inert gas protection, in -20~150 DEG C of 2~8h of reaction, TLC, which tracks to reaction, to be terminated, and reaction solution is through water
Wash, dry, be concentrated after be dissolved in solvent H, under inert gas protection, be added dropwise borane reagent at -40~30 DEG C, reaction 1~
40wt%~60wt% sodium hydrate aqueous solution and 30wt% hydrogen peroxide are added after 3h, reacts 1~4h, TLC tracks to reaction knot
Beam obtains bromobenzene containing alcohol ether shown in formula VIII through washing, drying, concentration.
Step (7) is shown in the formula VIII that obtains biphenylboronic acid and step (6) shown in formula V that step (4) obtains containing alcohol ether
Bromobenzene deaerates through room temperature in solvent I protect 0.5~2h of stirring under alkaline condition, palladium-containing catalyst is then added, then be placed in
2-8h is reacted at 60~120 DEG C, TLC tracks to end of reaction, and reaction solution is washed, is concentrated, and obtains terphenyl second shown in formula Ⅸ
Alcohol.
Step (8) is that terphenyl ethyl alcohol shown in formula Ⅸ that step (7) obtains is dissolved in solvent J, alkali is added, and use inertia
Gas degassing protection, is added dropwise methacrylic chloride, natural 1~4h of temperature reaction, TLC, which is tracked to, to have reacted at -30~20 DEG C
Finish, reaction solution obtains terphenyl acrylate shown in formula Ⅹ through liquid separation, washing, drying, concentration.
Step (9) is that terphenyl acrylate shown in formula Ⅹ that step (8) obtains is dissolved in solvent K, by acidic materials
It is added drop-wise in reaction system and stirs at -15~35 DEG C, 2~6h is then reacted at 25~30 DEG C, TLC tracks fully reacting
Afterwards, reaction solution obtains final product liquid crystal material shown in formula Ⅺ through liquid separation, washing, drying, concentration.
The beneficial effects of the present invention are: raw material o ethyl aniline and salicylaldhyde are cheap and easy to get, wherein adjacent ethyl
Aniline protects upper bromine, Suzuki to be coupled by acetyl group, halogen, lithiumation boration obtain intermediate biphenyl in deprotection diazotising
Boric acid；Meanwhile during salicylaldhyde is reacted through upper bromine, Williamson etherification reaction, Wittig, hydroboration-oxidation obtains
Mesosome bromobenzene containing alcohol ether, biphenylboronic acid and bromobenzene containing alcohol ether are coupled through Suzuki, obtain liquid crystal material at ester, deprotection.
The solvent that the present invention uses more environmental protection, easy controlled operation, risk factor is less, and Suzuki coupling reaction does not generate more
The coupling impurity for replacing halides to generate, one-step reaction selectivity are high.
The present invention uses convergence type highway route design, and total recovery is up to 40% or more, compared with the route high income of patent report, at
This lower, better economic benefit.
Specific embodiment
The present invention will be described in detail below with reference to specific embodiments:
A kind of preparation method of liquid crystal material, the solvent A in step (1) are acetic acid, methylene chloride, N, N- dimethyl formyl
The mixture of one or more of amine arbitrary proportion；The volumetric usage of solvent A is with the substance of o ethyl aniline shown in formula I
Amount be calculated as 0.1~0.5ml/mmol；O ethyl aniline shown in acetic anhydride, bromine, hydrogen peroxide, sodium hydrogensulfite and formula I rubs
You are than being respectively (1~2): 1, (0.5~1): 1, (1~4): 1, (0.1~1): 1；
Alkali used in step (2) neutral and alkali condition is sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, cesium carbonate, fluorination
The mixture of one or more of potassium, sodium fluoride, potassium phosphate, sodium phosphate arbitrary proportion；Solvent B is tetrahydrofuran, second
One or both of glycol dimethyl ether, n,N-Dimethylformamide, toluene, ethyl alcohol, methanol, Isosorbide-5-Nitrae-dioxane, acetonitrile, water
The mixed solvent of any of the above ratio, the volumetric usage of solvent B is denoted as 1 with the amount of the substance of acetylamino bromobenzene shown in formula II~
2ml/mmol；Palladium-containing catalyst is tetra-triphenylphosphine palladium, [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride, three (two Asias
Benzylacetone) it is two palladiums, chlorination Allylpalladium dimer, bis- (dibenzalacetone) palladiums, two (triphenylphosphine) palladium chlorides, double
The mixture of one or more of (tricyclohexyl phosphine) palladium chloride arbitrary proportion；To amyl phenyl boric acid, alkaline condition
The molar ratio of acetylamino bromobenzene shown in alkali used, palladium-containing catalyst and formula II is respectively (1~1.2): 1, (2~5): 1,
(0.00001~0.001): 1.
Solvent C in step (3) is tetrahydrofuran, 2- methyltetrahydrofuran, acetic acid, ethyl acetate, Isosorbide-5-Nitrae-dioxane
One or more of arbitrary proportion mixture；When producing biphenyl bromine, sulfuric acid, sodium nitrite, cuprous bromide, hydrobromic acid
Molar ratio with acetylamino biphenyl shown in formula III is respectively (1~4): 1, (1~1.1): 1, (1~1.5): 1, (1~4): 1；
When producing biphenyl iodine, the molar ratio of acetylamino biphenyl shown in hydrochloric acid/sulfuric acid, sodium nitrite, potassium iodide and formula III is respectively (1
~5): 1, (1~1.1): 1, (1~1.5): 1；
Solvent D in step (4) be one of tetrahydrofuran, 2- methyltetrahydrofuran, glycol dimethyl ether or they
Respectively with the mixed liquor of hexane；Boron alkyl acid esters be selected from trimethylborate, triethyl borate, triproylborate, butyl borate,
Triisopropyl borate ester, methanol pinacol borate, ethyl alcohol pinacol borate, propyl alcohol pinacol borate, isopropanol pinacol
Borate, methanol neopentyl glycol borate, ethyl alcohol neopentyl glycol ester borate, propyl alcohol neopentyl glycol ester borate, butanol new penta
Any one or a few mixture in glycol borate ester or isopropanol neopentyl glycol borate；The volumetric usage of solvent D is
4~10 times of biphenyl halides quality shown in formula IV；Mole of biphenyl halides shown in boron alkyl acid esters, n-BuLi and formula IV
Than being respectively (1~5): 1, (1~2): 1；
Solvent E in step (5) is one of n,N-Dimethylformamide, methylene chloride, acetonitrile, 1,2- dichloroethanes
Or two or more arbitrary proportion mixtures, the volumetric usage of solvent E are denoted as 1 with the amount of the substance of salicylaldhyde shown in formula VI
~2ml/mmol；Solvent F is toluene, 1,2- dichloroethanes, n,N-Dimethylformamide, N, N- diethylformamide, dimethyl
The mixed solvent of one or more of sulfoxide, N-Methyl pyrrolidone arbitrary proportion；The volumetric usage of solvent F is with formula VI
The amount of the substance of shown salicylaldhyde is denoted as 0.1~1ml/mmol；Alkali is sodium carbonate, potassium carbonate, lithium carbonate, bicarbonate
One or more of sodium, cesium carbonate, potassium fluoride, sodium fluoride, potassium phosphate, sodium phosphate arbitrary proportion mixture；Bromine,
Alkali, organic bromide R1The molar ratio of salicylaldhyde shown in-Br, sodium sulfite and formula VI is respectively (1~1.5): 1, (1
~4): 1, (1~1.5): 1, (0.1~1): 1；
Methyl Wittig reagent in step (6) is selected from methyltriphenylphosphonium bromide, methyl triphenyl phosphorus chloride or methyl
One of triphenyl phosphonium iodide phosphine, alkali used in alkaline condition are potassium tert-butoxide, sodium tert-butoxide, sodium methoxide, potassium methoxide, ethyl alcohol
Sodium, potassium ethoxide, sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, cesium carbonate, potassium fluoride, sodium fluoride, potassium phosphate, in sodium phosphate
One or more kinds of arbitrary proportions mixture；Solvent G be toluene, 1,2- dichloroethanes, n,N-Dimethylformamide, N,
N- diethylformamide, dimethyl sulfoxide, the one or more kinds of arbitrary proportions of Isosorbide-5-Nitrae-dioxane mixed solvent, solvent
The volumetric usage of G is denoted as 0.5~1ml/mmol with the amount of the substance of ether-containing bromobenzene shown in formula VII；Borane reagent is boranepyridine network
One of object, borine trimethylamine complex, borine tetrahydrofuran complex or borine morpholine complex compound are closed, solvent H is dichloro
One or more of methane, 1,2- dichloroethanes, chloroform, n-hexane, tetrahydrofuran, 2- methyltetrahydrofuran are appointed
The volumetric usage of meaning ratio mixed solvent, solvent H is denoted as 0.5~1ml/mol with the amount of the substance of ether-containing bromobenzene shown in formula VII；Drop
Adding sodium hydroxide and the temperature of hydrogen peroxide are -40~30 DEG C, and 1~4h is reacted at reaction temperature -40~30 DEG C；Methyl Wittig
The molar ratio of ether-containing bromobenzene shown in reagent, alkali, borane reagent, sodium hydroxide, hydrogen peroxide and formula VII is respectively (1~1.5): 1, (1
~4): 1, (1~4): 1, (1~5): 1, (1~5): 1；
Alkali used in step (7) neutral and alkali condition is sodium carbonate, potassium carbonate, lithium carbonate, sodium bicarbonate, cesium carbonate, fluorination
The mixture of one or more of potassium, sodium fluoride, potassium phosphate, sodium phosphate arbitrary proportion；Solvent I is tetrahydrofuran, second
One or both of glycol dimethyl ether, n,N-Dimethylformamide, toluene, ethyl alcohol, methanol, Isosorbide-5-Nitrae-dioxane, acetonitrile, water
The mixed solvent of any of the above ratio, the volumetric usage of solvent I is denoted as 1 with the amount of the substance of the bromobenzene containing alcohol ether shown in formula VIII~
2ml/mmol, palladium-containing catalyst are tetra-triphenylphosphine palladium, [1,1 '-bis- (diphenylphosphino) ferrocene] palladium chloride, three (two Asias
Benzylacetone) it is two palladiums, chlorination Allylpalladium dimer, bis- (dibenzalacetone) palladiums, two (triphenylphosphine) palladium chlorides, double
One or more of (tricyclohexyl phosphine) palladium chloride, 1,1 '-(double-tert. butylphosphino) ferrocene palladium chloride are any
The mixture of ratio；Biphenylboronic acid shown in palladium-containing catalyst, formula V, the bromobenzene containing alcohol ether shown in alkali and formula VIII molar ratio be respectively
(0.00001~0.001): 1, (0.8~1.2): 1, (1~5): 1；
Alkali used in step (8) is dimethylamine, trimethylamine, diethylamine, triethylamine, tri-n-butylamine, N, N- dimethyl pyrazole
Pyridine, methylphenylamine, n,N-Dimethylaniline, pyridine one or more kinds of arbitrary proportion mixtures；Solvent J be toluene,
Methylene chloride, chloroform, n-hexane, acetonitrile, 1,2- dichloroethanes, n,N-Dimethylformamide, Isosorbide-5-Nitrae-dioxane one
The mixed solvent of kind or two or more arbitrary proportions, the volumetric usage of solvent J is with the amount of the substance of terphenyl ethyl alcohol shown in formula Ⅸ
It is denoted as 4~6ml/mol；The molar ratio of terphenyl ethyl alcohol shown in methacrylic chloride, alkali and formula Ⅸ is respectively (1.5~3): 1, (1
~5): 1, the temperature that methacrylic chloride is added dropwise is -20~0 DEG C, and 1~4h is reacted at 0~30 DEG C；
Solvent K in step (9) is methanol, in ethyl alcohol, tetrahydrofuran, 2- methyltetrahydrofuran, Isosorbide-5-Nitrae-dioxane
One or more kinds of arbitrary proportion mixed solvents, the volumetric usage of solvent K are terphenyl acrylate quality shown in formula Ⅹ
10~15 times, acidic materials are the mixture of one or both of hydrochloric acid, p-methyl benzenesulfonic acid, solid acid arbitrary proportion, acid
The molar ratio of terphenyl acrylate shown in substance and formula Ⅹ is (1.1~1.5): 1；Acidic materials are added dropwise at -15~30 DEG C.
Embodiment 1, a kind of preparation method of liquid crystal material carry out as follows:
(1) preparation of 2- ethyl -4- acetyl bromide aniline:
O ethyl aniline 96.9g (0.8mol), acetic acid 232ml are added into 1L there-necked flask, is cooled to 20 after stirring and dissolving
DEG C, be added dropwise acetic anhydride 102.1g (1mol), stir 1h after dripping, be cooled to 10 DEG C, be added dropwise bromine 67.2g (0.42mol) and
After stirring 3h, the 150ml for containing sodium hydrogensulfite 21.8g (0.21mol) is added in hydrogen peroxide (30wt%) 95.2g (0.84mol)
Aqueous solution steams most of solvent, through suction filtration, washing, drying, obtains white solid i.e. 2- ethyl -4- acetyl bromide aniline
183.9g, yield 95%；
The preparation of (2) 4 '-amyl -3- ethyl -4- acetylamino biphenyl:
2- ethyl -4- acetyl bromide aniline 96.9g (0.4mol) is added into 3L there-necked flask, to amyl phenyl boric acid 76.8g
(0.4mol), toluene 400ml, n,N-Dimethylformamide 120ml, nitrogen protection and displaced air for several times, when being heated to 50 DEG C
The 100ml aqueous solution for containing potassium fluoride 92.8g (1.6mol) is added, tetrakis triphenylphosphine palladium catalyst 0.04g is then added
(0.000035mol) after being heated to back flow reaction 3h, is separately added into 100ml water and the stirring liquid separation of 200ml toluene, through extraction, water
It washes, dry, column chromatography for separation concentration obtains white solid i.e. 4 '-amyl -3- ethyl -4- acetylamino biphenyl 116.4g, yield
It is 94%；
The preparation of (3) 4 '-amyl -3- ethyl -4- bromo biphenyls:
Be added in 1L there-necked flask 4 '-amyl -3- ethyl -4- acetylamino biphenyl 61.9g (0.2mol), acetic acid 200ml,
Aqueous sulfuric acid 117.6g (0.6mol, mass fraction 50wt%) after being heated to reflux 2h, stops heating, is cooled to -10 DEG C,
The 40ml aqueous solution for containing sodium nitrite 14.5g (0.21mol) is added dropwise；Again into another 1L there-necked flask, cuprous bromide is added
31.5g (0.22mol), hydrobromic acid aqueous solution 81g (0.4mol, mass fraction 40wt%) and 60ml water, heating water bath is extremely
50 DEG C, the diazonium salt drop prepared is added in cuprous bromide-hydrobromic acid solution, drips reaction 2h, after fully reacting, warp
It is concentrated under reduced pressure after filtering, extraction, liquid separation, washing, drying, column chromatography for separation obtains light yellow oil i.e. 4 '-amyl -3- second
Base -4- bromo biphenyl 61.6g, yield 93%；
Either, the preparation of (3) 4 '-amyl -3- ethyl -4- iodine biphenyl:
Be added in 1L there-necked flask 4 '-amyl -3- ethyl -4- acetylamino biphenyl 61.9g (0.2mol), acetic acid 200ml,
Aqueous hydrochloric acid solution 205.3g (0.9mol, mass fraction 16wt%) after being heated to reflux 2h, stops heating, is cooled to -10 DEG C,
The 40ml aqueous solution for containing sodium nitrite 14.5g (0.21mol) is added dropwise；Again into another 1L there-necked flask, potassium iodide 34.9g is added
The stirring of (0.21mol) and 75ml water, ice-water bath are cooled to 0 DEG C, the diazonium salt drop prepared are added to liquor kalii iodide, are added dropwise
Complete reaction 2h after fully reacting, is concentrated under reduced pressure, column chromatography for separation obtains pale yellowish oil after extraction, liquid separation, washing, drying
Object i.e. 4 '-amyl -3- ethyl -4- iodine biphenyl 66.6g, yield 88%；
The preparation of (4) 4 '-amyl -3- ethyl -4- biphenylboronic acids:
Anhydrous tetrahydro furan 150ml and 4 '-amyl -3- ethyl -4- bromo biphenyl is added into a 500ml there-necked flask
33.1g (0.1mol), stirs evenly, and is cooled to -80 DEG C under nitrogen protection, heat preservation be added dropwise concentration be 2.7mol/L n-BuLi oneself
After -80 DEG C of stirring 0.5h of rear temperature control are added dropwise, triisopropyl borate ester 21g is added dropwise in alkane solution 40.7ml (0.11mol)
(0.11mol) warms naturally to -30 DEG C after -80 DEG C of reaction 2h of rear temperature control are added dropwise, and control drop speed is 1~3 drop/sec, is added
30ml concentrated hydrochloric acid is dissolved in the aqueous solution of 70ml water, stirs liquid separation, extraction, washing and drying, concentration and separation after 1h, obtains 4 '-amyls-
3- ethyl -4- biphenylboronic acid 25.2g, yield 85%；
Either, 4 '-amyl -3- ethyl -4- are replaced with 4 '-amyl -3- ethyl -4- iodine biphenyl 37.8g (0.1mol)
Bromo biphenyl 33.1g (0.1mol), remaining step are same as above, and finally obtain 4 '-amyl -3- ethyl -4- biphenylboronic acid 27.5g, yield
It is 93%；
1H-NMR (400MHz, CDCl3) δ 7.94 (d, J=7.5Hz, 1H), 7.58-7.54 (m, 2H), 7.51 (q, J=
1.2Hz, 1H), 7.41 (dd, J=7.5,2.0Hz, 1H), 7.29-7.25 (m, 2H), 2.69-2.62 (m, 4H), 1.66-1.57
(m, 4H), 1.30 (td, J=4.8,4.2,2.8Hz, 4H), 1.24 (t, J=8.0Hz, 3H), 0.92-0.87 (m, 3H)；
(5) the bromo- 2-[(tertiary butyl dimethyl Si base of 5-) ethyoxyl] benzaldehyde preparation:
Salicylaldhyde 48.8g (0.4mol), methylene chloride 400ml, stirring cooling are added into a 1L there-necked flask
To 0 DEG C, bromine 70.4g (0.44mol) solution for being dissolved in 70ml methylene chloride is added dropwise, reacts 6h, addition contains sodium sulfite
The 200ml aqueous solution of 25.2g (0.2mol) obtains crude product containing bromo-derivative after liquid separation, extraction, washing, drying, N, N- is added
Potassium carbonate 110.4g (0.8mol), (2- bromine oxethyl)-tert-butyl two is then added in dimethylformamide 120ml stirring and dissolving
Methyl-monosilane 114.6g (0.48mol), nitrogen protection and displaced air for several times, are heated to back flow reaction 3h, after fully reacting, point
Not Jia Ru 100ml water and 100ml ethyl acetate stir liquid separation, through extraction, washing, drying, column chromatography for separation is concentrated to get pale yellow
The bromo- 2-[(tertiary butyl dimethyl Si base of color oil liquid, that is, 5-) ethyoxyl] benzaldehyde 133.7g, yield 93%；
(6) the bromo- 2-[(tertiary butyl dimethyl Si base of 5-) ethyoxyl] phenylethanol preparation:
The bromo- 2-[(tertiary butyl dimethyl Si base of 5- is added into 1L there-necked flask) ethyoxyl] benzaldehyde 71.9g
(0.2mol), methyltriphenylphosphonium bromide 85.7g (0.24mol), potassium tert-butoxide 33.7g (0.3mol), Isosorbide-5-Nitrae-dioxane
For several times, heating reflux reaction 6h after fully reacting, is separately added into 100ml water and 100ml for 144ml, nitrogen protection and displaced air
Ethyl acetate stirs liquid separation, is concentrated to get crude product through extraction washing, drying, and the dissolution of 144ml tetrahydrofuran, ice-water bath cooling is added
And with nitrogen protection, control drop speed is 1~3 drop/sec, and borine tetrahydrofuran solution 200ml (containing borine 0.2mol) is added drop-wise to
In reaction solution, after insulation reaction 2h, successively it is separately added into the 50ml aqueous solution containing sodium hydroxide 28g (0.7mol) and 68ml is bis-
Oxygen water (30wt%), natural temperature reaction 2h are separately added into 100ml water and the stirring point of 100ml methylene chloride after reaction
Liquid, through extraction, washing and drying, column chromatography for separation obtains the bromo- 2-[(tertiary butyl dimethyl Si base of light yellow oil liquid i.e. 5-) second
Oxygroup] phenylethanol 66.1g, yield 88%；
1H-NMR (400MHz, CDCl3) δ 7.27 (dd, J=1.9,1.1Hz, 1H), 7.08 (dd, J=7.5,2.0Hz,
1H), 6.71 (d, J=7.4Hz, 1H), 4.50 (t, J=7.3Hz, 2H), 4.21 (t, J=7.2Hz, 2H), 3.89 (td, J=
7.5,5.0Hz, 2H), 2.61 (t, J=5.0Hz, 1H), 2.01 (td, J=7.5,1.0Hz, 2H), 1.07 (s, 9H), 0.08 (s,
6H)；
(7) 2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] three
Biphenyl -3- base } ethyl alcohol preparation:
The bromo- 2-[(tertiary butyl dimethyl Si base of 5- is added into 500ml there-necked flask) ethyoxyl] phenylethanol 75.1g
(0.2mol), 4 '-amyl -3- ethyl -4- biphenylboronic acid 59.2g (0.2mol), toluene 200ml, n,N-Dimethylformamide
60ml, nitrogen protection and displaced air for several times, it is water-soluble to be heated to 50ml of the addition containing potassium fluoride 46.4g (0.8mol) at 50 DEG C
Liquid is then added tetrakis triphenylphosphine palladium catalyst 0.04g (0.000035mol) and is separately added into after being heated to back flow reaction 3h
50ml water and 100ml toluene stir liquid separation, and through extraction, washing, drying, column chromatography for separation concentration obtains oil liquid i.e. 2- { 4-[2-
(tertiary butyl dimethyl Si base) ethyoxyl] -2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base } ethyl alcohol
99.5g, yield 91%；
(8) 2- methacrylic acid -2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -2 '-ethyls -4 "-amyl -
[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate preparation:
Into 500ml there-necked flask, addition 2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] and -2 '-ethyls -4 "-penta
Base-[1,1 '；4 ', 1 "] terphenyl -3- base } ethyl alcohol 27.3g (0.05mol), 4-dimethylaminopyridine 0.6g (0.005mol), three
Ethamine 7.6g (0.075mol), 250ml methylene chloride are cooled to 5 DEG C, and nitrogen protection, control drop speed is 1~3 drop/sec, by first
Base acryloyl chloride 7.8g (0.075mol) is added in reaction solution, drips nature temperature reaction 4h, washes after reaction, is dry
Dry, filtering, column chromatographic purifying are concentrated to get limpid colourless oil liquid i.e. 2- methacrylic acid -2- { 4-[2- (tert-butyldimethyl silyl
Oxygroup) ethyoxyl] -2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate 27.7g, yield 90%；
(9) 2- methacrylic acid 2-[2 '-ethyl -4- (2- hydroxyl-oxethyl) -4 "-amyl-[1,1 '；4 ', 1 "] three
Benzene -3- base] ethyl ester preparation:
Into 500ml there-necked flask be added 2- methacrylic acid -2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -
2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate 12.3g (0.02mol), with the Isosorbide-5-Nitrae-two of 150ml
After six ring stirring and dissolving of oxygen, it is cooled to 0 DEG C, control drop speed is 1~3 drop/sec, will contain 2.2ml (0.024mol) concentrated hydrochloric acid
10ml aqueous solution is added drop-wise in reaction solution, after insulated and stirred reacts 1h, warms naturally to 25 DEG C of reaction 3h, after fully reacting respectively
50ml ethyl acetate and 50ml water is added, through liquid separation, extraction, washing, drying, column chromatographic purifying is concentrated to get white solid i.e.
2- methacrylic acid 2-[2 '-ethyl -4- (2- hydroxyl-oxethyl) -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base] ethyl
Ester 9.4g, yield 94%.
1H-NMR(400MHz,CDCl3) δ=7.54ppm (d, J=8.1Hz, 2H), 7.50 (d, J=1.8Hz, 1H), 7.41
(dd, J=7.9,1.9Hz, 1H), 7.24 (d, J=8Hz, 2H), 7.20 (d, J=7.8Hz, 1H), 7.18 (dd, J=8.2,
2.2Hz, 1H), 7.13 (d, J=2.1Hz, 1H), 6.89 (d, J=8.2Hz, 1H), 6.12 (s, 1H), 5.55 (s, 1H), 4.40
(t, J=8Hz, 2H), 4.13 (t, J=4Hz, 2H), 4.02 (t, J=4Hz, 2H), 3.04 (t, J=7.6Hz, 2H), 2.88 (s,
1H), 2.65 (m, 4H), 1.93 (s, 3H), 1.66 (m, 2H), 1.36 (m, 4H), 1.14 (t, J=7.5Hz, 3H), 0.91 (t, J
=6.9Hz, 3H).
Embodiment 2, a kind of preparation method of liquid crystal material carry out as follows:
(1) preparation of 2- ethyl -4- acetyl bromide aniline:
O ethyl aniline 96.9g (0.8mol), methylene chloride 400ml are added into 1L there-necked flask, cools down after stirring and dissolving
It to 20 DEG C, is added dropwise acetic anhydride 81.6g (0.8mol), stirs 1h after dripping, be cooled to 10 DEG C, be added dropwise bromine 64g (0.4mol)
With hydrogen peroxide (30wt%) 90.7g (0.8mol), after stirring 3h, the 150ml for containing sodium hydrogensulfite 8.3g (0.08mol) is added
Aqueous solution steams most of solvent, through suction filtration, washing, drying, obtains white solid i.e. 2- ethyl -4- acetyl bromide aniline
180.1g yield 93%；
The preparation of (2) 4 '-amyl -3- ethyl -4- acetylamino biphenyl:
2- ethyl -4- acetyl bromide aniline 96.9g (0.4mol) is added into 3L there-necked flask, to amyl phenyl boric acid 80.7g
(0.42mol), toluene 400ml, n,N-Dimethylformamide 120ml, nitrogen protection and displaced air for several times, when being heated to 50 DEG C
The 339ml aqueous solution for containing potassium phosphate 339.7g (1.6mol) is added, bis- (tricyclohexyl phosphine) palladium chloride catalysis are then added
Agent 0.295g (0.0004mol) after being heated to back flow reaction 3h, is separately added into 100ml water and the stirring liquid separation of 200ml toluene, warp
Extraction, washing, drying, column chromatography for separation concentration, obtain white solid i.e. 4 '-amyl -3- ethyl -4- acetylamino biphenyl
117.6g yield 95%；
The preparation of (3) 4 '-amyl -3- ethyl -4- bromo biphenyls:
Be added in 1L there-necked flask 4 '-amyl -3- ethyl -4- acetylamino biphenyl 61.9g (0.2mol), acetic acid 200ml,
Aqueous sulfuric acid 39.2g (0.2mol, mass fraction 50wt%) after being heated to reflux 2h, stops heating, is cooled to -10 DEG C, drop
Add the 36ml aqueous solution containing sodium nitrite 13.8g (0.2mol)；Again into another 1L there-necked flask, cuprous bromide 28.7g is added
(0.2mol), hydrobromic acid aqueous solution 40.5g (0.2mol, mass fraction 40wt%) and 60ml water, heating water bath to 50 DEG C,
The diazonium salt drop prepared is added in cuprous bromide-hydrobromic acid solution, reaction 2h is dripped, after fully reacting, filtered,
It is concentrated under reduced pressure after extraction, liquid separation, washing, drying, column chromatography for separation obtains light yellow oil i.e. 4 '-amyl -3- ethyl -4-
Bromo biphenyl 60.3g, yield 91%；
Either, the preparation of (3) 4 '-amyl -3- ethyl -4- iodine biphenyl:
Be added in 1L there-necked flask 4 '-amyl -3- ethyl -4- acetylamino biphenyl 61.9g (0.2mol), acetic acid 200ml,
Aqueous hydrochloric acid solution 91.3g (0.4mol, mass fraction 16wt%) after being heated to reflux 2h, stops heating, is cooled to -10 DEG C, drop
Add the 36ml aqueous solution containing sodium nitrite 13.8g (0.2mol)；Again into another 1L there-necked flask, potassium iodide 33.2g is added
The stirring of (0.2mol) and 70ml water, ice-water bath are cooled to 0 DEG C, the diazonium salt drop prepared are added to liquor kalii iodide, are added dropwise
Complete reaction 2h after fully reacting, is concentrated under reduced pressure, column chromatography for separation obtains pale yellowish oil after extraction, liquid separation, washing, drying
Object i.e. 4 '-amyl -3- ethyl -4- iodine biphenyl 65.1g, yield 86%；
The preparation of (4) 4 '-amyl -3- ethyl -4- biphenylboronic acids:
Anhydrous 2- methyltetrahydrofuran 150ml and 4 '-amyl -3- ethyl -4- bromine connection is added into a 500ml there-necked flask
Benzene 33.1g (0.1mol), stirs evenly, and -80 DEG C is cooled under nitrogen protection, it is 2.7mol/L n-BuLi that concentration, which is added dropwise, in heat preservation
After -80 DEG C of stirring 0.5h of rear temperature control are added dropwise, isopropanol pinacol borate is added dropwise in hexane solution 37ml (0.1mol)
18.6g (0.1mol) warms naturally to -30 DEG C after -80 DEG C of reaction 2h of rear temperature control are added dropwise, and control drop speed is 1~3 drop/sec,
The aqueous solution that 30ml concentrated hydrochloric acid is dissolved in 70ml water is added, stirs liquid separation, extraction, washing and drying, concentration and separation after 1h, obtains 4 '-
Amyl -3- ethyl -4- biphenylboronic acid 24.9g, yield 84%；
Either, 4 '-amyl -3- ethyl -4- are replaced with 4 '-amyl -3- ethyl -4- iodine biphenyl 37.8g (0.1mol)
Bromo biphenyl 33.1g (0.1mol), remaining step are same as above, and finally obtain 4 '-amyl -3- ethyl -4- biphenylboronic acid 26.9g, yield
It is 91%；
(5) the bromo- 2-[(tertiary butyl dimethyl Si base of 5-) ethyoxyl] benzaldehyde preparation:
Salicylaldhyde 48.8g (0.4mol), methylene chloride 400ml, stirring cooling are added into a 1L there-necked flask
To 0 DEG C, bromine 65.5g (0.41mol) solution for being dissolved in 64ml methylene chloride is added dropwise, reacts 6h, is added and contains sodium sulfite 4g
The 32ml aqueous solution of (0.04mol) obtains crude product containing bromo-derivative after liquid separation, extraction, washing, drying, N- methyl pyrrole is added
Potassium fluoride 46.4g (0.8mol), (2- bromine oxethyl)-t-butyldimethyl silane is then added in pyrrolidone 120ml stirring and dissolving
95.5g (0.4mol), nitrogen protection and displaced air for several times, are heated to back flow reaction 3h, after fully reacting, are separately added into
100ml water and 100ml ethyl acetate stir liquid separation, and through extraction, washing, drying, column chromatography for separation is concentrated to get light yellow oil liquid
That is the bromo- 2-[(tertiary butyl dimethyl Si base of 5-) ethyoxyl] benzaldehyde 132.3g, yield 92%；
(6) the bromo- 2-[(tertiary butyl dimethyl Si base of 5-) ethyoxyl] phenylethanol preparation:
The bromo- 2-[(tertiary butyl dimethyl Si base of 5- is added into 1L there-necked flask) ethyoxyl] benzaldehyde 71.9g
(0.2mol), methyl triphenyl phosphorus chloride 62.5g (0.2mol), sodium methoxide 21.6g (0.4mol), Isosorbide-5-Nitrae-dioxane 144ml,
Simultaneously for several times, heating reflux reaction 6h after fully reacting, is separately added into 100ml water and 100ml acetic acid second to displaced air to nitrogen protection
Ester stirs liquid separation, is concentrated to get crude product through extraction washing, drying, the dissolution of 144ml tetrahydrofuran is added, ice-water bath cools down and uses nitrogen
Gas shielded, control drop speed is 1~3 drop/sec, and borine-trimethylamine complex 29.2g (0.4mol) is dissolved in 100ml tetrahydrofuran
In, it is added drop-wise in reaction solution, after insulation reaction 2h, is successively separately added into the 25ml aqueous solution containing sodium hydroxide 8g (0.2mol)
With 22.6ml hydrogen peroxide (30wt%), natural temperature reaction 2h is separately added into 100ml water and 100ml dichloromethane after reaction
Alkane stirs liquid separation, and through extraction, washing and drying, column chromatography for separation obtains the bromo- 2-[(tert-butyldimethyl silyl of light yellow oil liquid i.e. 5-
Oxygroup) ethyoxyl] phenylethanol 64.6g, yield 86%；
(7) 2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] three
Biphenyl -3- base } ethyl alcohol preparation:
The bromo- 2-[(tertiary butyl dimethyl Si base of 5- is added into 500ml there-necked flask) ethyoxyl] phenylethanol 75.1g
(0.2mol), 4 '-amyl -3- ethyl -4- biphenylboronic acid 53.3g (0.18mol), toluene 200ml, n,N-Dimethylformamide
60ml, nitrogen protection and displaced air for several times, it is water-soluble to be heated to 50ml of the addition containing potassium carbonate 55.3g (0.4mol) at 50 DEG C
Two (triphenylphosphine) palladium chloride catalyst 0.0014g (0.000002mol) are then added in liquid, after being heated to back flow reaction 3h,
It is separately added into 50ml water and the stirring liquid separation of 100ml toluene, through extraction, washing, drying, column chromatography for separation concentration obtains oil liquid i.e.
2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] and -2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base }
Ethyl alcohol 88.6g, yield 90%；
(8) 2- methacrylic acid -2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -2 '-ethyls -4 "-amyl -
[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate preparation:
Into 500ml there-necked flask, addition 2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] and -2 '-ethyls -4 "-penta
Base-[1,1 '；4 ', 1 "] terphenyl -3- base } ethyl alcohol 27.3g (0.05mol), 4-dimethylaminopyridine 0.6g (0.005mol), three
Ethamine 5.1g (0.05mol), Isosorbide-5-Nitrae-dioxane 250ml are cooled to 5 DEG C, and nitrogen protection, control drop speed is 1~3 drop/sec, drop
Methylate acryloyl chloride 7.8g (0.075mol) drips nature temperature reaction 4h, washes after reaction, is dry, filtering, column
Chromatographic purifying is concentrated to get limpid colourless oil liquid i.e. 2- methacrylic acid -2- { 4-[2- (tertiary butyl dimethyl Si base) ethoxy
Base] -2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate 27.1g, yield 88%；
(9) 2- methacrylic acid -2-[2 '-ethyl -4- (2- hydroxyl-oxethyl) -4 "-amyl-[1,1 '；4 ', 1 "] three
Benzene -3- base] ethyl ester preparation:
Into 500ml there-necked flask be added 2- methacrylic acid -2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -
2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate 12.3g (0.02mol), with 150ml tetrahydrofuran
After stirring and dissolving, it is cooled to 0 DEG C, control drop speed is 1~3 drop/sec, will contain the 10ml of p-methyl benzenesulfonic acid 4.1g (0.024mol)
Aqueous solution is added drop-wise in reaction solution, after insulated and stirred reacts 1h, is warmed naturally to 25 DEG C of reaction 3h, is separately added into after fully reacting
50ml ethyl acetate and 50ml water, through liquid separation, extraction, washing, drying, column chromatographic purifying is concentrated to get white solid i.e. 2- first
Base acrylic acid -2-[2 '-ethyl -4- (2- hydroxyl-oxethyl) -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base] ethyl ester
9.5g, yield 95%.
Embodiment 3, a kind of preparation method of liquid crystal material carry out as follows:
(1) preparation of 2- ethyl -4- acetyl bromide aniline:
O ethyl aniline 96.9g (0.8mol), acetic acid 400ml are added into 3L there-necked flask, is cooled to 20 after stirring and dissolving
DEG C, be added dropwise acetic anhydride 114.4g (1.1mol), stir 1h after dripping, be cooled to 10 DEG C, be added dropwise bromine 95.9g (0.6mol) and
After stirring 3h, the 200ml water for containing sodium hydrogensulfite 83.3g (0.8mol) is added in hydrogen peroxide (30wt%) 272g (2.4mol)
Solution steams most of solvent, through suction filtration, washing, drying, obtains white solid i.e. 2- ethyl -4- acetyl bromide aniline
185.9g, yield 96%；
The preparation of (2) 4 '-amyl -3- ethyl -4- acetylamino biphenyl:
2- ethyl -4- acetyl bromide aniline 96.9g (0.4mol) is added into 3L there-necked flask, to amyl phenyl boric acid 76.8g
(0.4mol), toluene 400ml, n,N-Dimethylformamide 120ml, nitrogen protection and displaced air for several times, when being heated to 50 DEG C
The 110ml aqueous solution for containing potassium carbonate 110.6g (0.8mol) is added, two (triphenylphosphine) palladium chloride catalyst are then added
0.0028g (0.000004mol) after being heated to back flow reaction 3h, is separately added into 110ml water and the stirring liquid separation of 200ml toluene, warp
Extraction, washing, drying, column chromatography for separation concentration, obtain white solid i.e. 4 '-amyl -3- ethyl -4- acetylamino biphenyl
111.4g yield 90%；
The preparation of (3) 4 '-amyl -3- ethyl -4- bromo biphenyls:
Be added in 1L there-necked flask 4 '-amyl -3- ethyl -4- acetylamino biphenyl 61.9g (0.2mol), acetic acid 200ml,
Aqueous sulfuric acid 117.6g (0.6mol, mass fraction 50wt%) after being heated to reflux 2h, stops heating, is cooled to -10 DEG C,
The 50ml aqueous solution for containing sodium nitrite 14.5g (0.21mol) is added dropwise；Again into another 1L there-necked flask, cuprous bromide is added
34.4g (0.24mol), hydrobromic acid aqueous solution 80.9g (0.4mol, mass fraction 40wt%) and 60ml water, heating water bath
To 50 DEG C, the diazonium salt drop prepared is added in cuprous bromide-hydrobromic acid solution, drips reaction 2h, after fully reacting,
It is concentrated under reduced pressure after filtering, extraction, liquid separation, washing, drying, column chromatography for separation obtains light yellow oil i.e. 4 '-amyl -3-
Ethyl -4- bromo biphenyl 62.9g, yield 95%；
Either, the preparation of (3) 4 '-amyl -3- ethyl -4- iodine biphenyl:
Be added in 1L there-necked flask 4 '-amyl -3- ethyl -4- acetylamino biphenyl 61.9g (0.2mol), acetic acid 200ml,
Aqueous hydrochloric acid solution 182.6g (0.8mol, mass fraction 16wt%) after being heated to reflux 2h, stops heating, is cooled to -10 DEG C,
The 50ml aqueous solution for containing sodium nitrite 14.5g (0.21mol) is added dropwise；Again into another 1L there-necked flask, potassium iodide 39.8g is added
The stirring of (0.24mol) and 80ml water, ice-water bath are cooled to 0 DEG C, the diazonium salt drop prepared are added to liquor kalii iodide, are added dropwise
Complete reaction 2h after fully reacting, is concentrated under reduced pressure, column chromatography for separation obtains pale yellowish oil after extraction, liquid separation, washing, drying
Object i.e. 4 '-amyl -3- ethyl -4- iodine biphenyl 67.3g, yield 89%；
The preparation of (4) 4 '-amyl -3- ethyl -4- biphenylboronic acids:
Anhydrous tetrahydro furan 150ml and 4 '-amyl -3- ethyl -4- bromo biphenyl is added into a 500ml there-necked flask
33.1g (0.1mol), stirs evenly, and is cooled to -80 DEG C under nitrogen protection, heat preservation be added dropwise concentration be 2.7mol/L n-BuLi oneself
After -80 DEG C of stirring 0.5h of rear temperature control are added dropwise, trimethylborate 20.8g is added dropwise in alkane solution 44.4ml (0.12mol)
(0.2mol) warms naturally to -30 DEG C after -80 DEG C of reaction 2h of rear temperature control are added dropwise, and control drop speed is 1~3 drop/sec, is added
30ml concentrated hydrochloric acid is dissolved in the aqueous solution of 70ml water, stirs liquid separation, extraction, washing and drying, concentration and separation after 1h, obtains 4 '-amyls-
3- ethyl -4- biphenylboronic acid 25.2g, yield 85%；
Either, 4 '-amyl -3- ethyl -4- are replaced with 4 '-amyl -3- ethyl -4- iodine biphenyl 37.8g (0.1mol)
Bromo biphenyl 33.1g (0.1mol), remaining step are same as above, and finally obtain 4 '-amyl -3- ethyl -4- biphenylboronic acid 27.2g, yield
92%；
(5) the bromo- 2-[(tertiary butyl dimethyl Si base of 5-) ethyoxyl] benzaldehyde preparation:
Salicylaldhyde 48.8g (0.4mol), methylene chloride 400ml, stirring cooling are added into a 1L there-necked flask
To 0 DEG C, bromine 76.7g (0.48mol) solution for being dissolved in 70ml methylene chloride is added dropwise, reacts 6h, is added and contains sodium sulfite 20g
The 300ml aqueous solution of (0.2mol) obtains crude product containing bromo-derivative after liquid separation, extraction, washing, drying, N, N- diformazan is added
Potassium fluoride 58g (1mol), (2- bromine oxethyl)-t-butyldimethyl silane is then added in base formamide 240ml stirring and dissolving
124.4g (0.52mol), nitrogen protection and displaced air for several times, are heated to back flow reaction 3h, after fully reacting, are separately added into
100ml water and 100ml ethyl acetate stir liquid separation, and through extraction, washing, drying, column chromatography for separation is concentrated to get light yellow oil liquid
That is the bromo- 2-[(tertiary butyl dimethyl Si base of 5-) ethyoxyl] benzaldehyde 133.7g, yield 93%；
(6) the bromo- 2-[(tertiary butyl dimethyl Si base of 5-) ethyoxyl] phenylethanol preparation:
The bromo- 2-[(tertiary butyl dimethyl Si base of 5- is added into 1L there-necked flask) ethyoxyl] benzaldehyde 71.9g
(0.2mol), methyl triphenyl phosphonium iodide 97.2g (0.24mol), potassium carbonate 55.2g (0.4mol), Isosorbide-5-Nitrae-dioxane
For several times, heating reflux reaction 6h after fully reacting, is separately added into 100ml water and 100ml for 144ml, nitrogen protection and displaced air
Ethyl acetate stirs liquid separation, is concentrated to get crude product through extraction washing, drying, and the dissolution of 144ml tetrahydrofuran, ice-water bath cooling is added
And with nitrogen protection, control drop speed is 1~3 drop/sec, and borane-pyridine complex 60ml (0.6mol) is dissolved in 100ml tetrahydro furan
It in muttering, is added drop-wise in reaction solution, after insulation reaction 2h, is successively separately added into the 80ml water containing sodium hydroxide 16g (0.4mol)
Solution and 45.2ml hydrogen peroxide (30wt%), natural temperature reaction 2h are separately added into 100ml water and 100ml bis- after reaction
Chloromethanes stirs liquid separation, and through extraction, washing and drying, column chromatography for separation obtains the bromo- 2-[(tert-butyl diformazan of light yellow oil liquid i.e. 5-
Base siloxy) ethyoxyl] phenylethanol 67.6g, yield 90%；
(7) 2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] three
Biphenyl -3- base } ethyl alcohol preparation:
The bromo- 2-[(tertiary butyl dimethyl Si base of 5- is added into 500ml there-necked flask) ethyoxyl] phenylethanol 75.1g
(0.2mol), 4 '-amyl -3- ethyl -4- biphenylboronic acid 62.2g (0.21mol), toluene 200ml, n,N-Dimethylformamide
60ml, nitrogen protection and displaced air for several times, are heated to that the 50ml water for containing potassium phosphate 169.8g (0.8mol) is added at 50 DEG C
Solution is then added bis- (tricyclohexyl phosphine) palladium chloride catalyst 0.00148g (0.000002mol), is heated to back flow reaction
After 3h, it is separately added into 50ml water and the stirring liquid separation of 100ml toluene, through extraction, washing, drying, column chromatography for separation concentration obtains oil
Liquid, that is, 2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] and -2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3-
Base } ethyl alcohol 101.7g, yield 93%；
(8) 2- methacrylic acid -2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -2 '-ethyls -4 "-amyl -
[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate preparation:
Into 500ml there-necked flask, addition 2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] and -2 '-ethyls -4 "-penta
Base-[1,1 '；4 ', 1 "] terphenyl -3- base } ethyl alcohol 27.3g (0.05mol), 4-dimethylaminopyridine 0.6g (0.005mol), pyrrole
Pyridine 7.9g (0.1mol), acetonitrile 250ml are cooled to 5 DEG C, and nitrogen protection, control drop speed is 1~3 drop/sec, and metering system is added dropwise
Acyl chlorides 13.1g (0.125mol) drips nature temperature reaction 4h, washes after reaction, is dry, filtering, column chromatographic purifying,
Be concentrated to get limpid colourless oil liquid i.e. 2- methacrylic acid -2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -2 '-second
Base -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate 27.7g, yield 90%；
(9) 2- methacrylic acid -2-[2 '-ethyl -4- (2- hydroxyl-oxethyl) -4 "-amyl-[1,1 '；4 ', 1 "] three
Benzene -3- base] ethyl ester preparation:
Into 500ml there-necked flask be added 2- methacrylic acid -2- 4-[2- (tertiary butyl dimethyl Si base) ethyoxyl] -
2 '-ethyls -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base } vinyl acetate 12.3g (0.02mol), is stirred with 150ml methanol
After dissolution, it is cooled to 0 DEG C, control drop speed is 1~3 drop/sec, will contain the water-soluble drop of 10ml of 2ml (0.022mol) concentrated hydrochloric acid
It is added in reaction solution, after insulated and stirred reacts 1h, warms naturally to 25 DEG C of reaction 3h, 50ml acetic acid is separately added into after fully reacting
Ethyl ester and 50ml water, through liquid separation, extraction, washing, drying, column chromatographic purifying is concentrated to get white solid i.e. 2- methacrylic acid-
2-[2 '-ethyl -4- (2- hydroxyl-oxethyl) -4 "-amyl-[1,1 '；4 ', 1 "] terphenyl -3- base] ethyl ester 9.2g, yield is
92%.
The total recovery of embodiment 1 is 95% × 94% × 93% × 85% × 93% × 88% × 91% × 90% × 94%
=44.48% or 95% × 94% × 88% × 93% × 93% × 88% × 91% × 90% × 94%=
46.05%.
The total recovery of embodiment 2 is 93% × 95% × 91% × 84% × 92% × 86% × 90% × 88% × 95%
=40.20% or 93% × 95% × 86% × 91% × 92% × 86% × 90% × 88% × 95%=
41.16%.
The total recovery of embodiment 3 is 96% × 90% × 95% × 85% × 93% × 90% × 93% × 90% × 92%
=44.97% or 96% × 90% × 89% × 92% × 93% × 90% × 93% × 90% × 92%=
45.60%.
It can be seen that total recovery of the invention can reach 40% or more, and the total recovery of comparative example 1 is 3.5%, comparative example
2 total recovery is 30%, and the present invention is compared with the route high income of patent report, and cost is relatively low, better economic benefit.
Final product nuclear magnetic spectrum of the present invention is as follows:
1H-NMR (400MHz, CDCl3) δ=7.54ppm (d, J=8.1Hz, 2H), 7.50 (d, J=1.8Hz, 1H), 7.41
(dd, J=7.9,1.9Hz, 1H), 7.24 (d, J=8Hz, 2H), 7.20 (d, J=7.8Hz, 1H), 7.18 (dd, J=8.2,
2.2Hz, 1H), 7.13 (d, J=2.1Hz, 1H), 6.89 (d, J=8.2Hz, 1H), 6.12 (s, 1H), 5.55 (s, 1H), 4.40
(t, J=8Hz, 2H), 4.13 (t, J=4Hz, 2H), 4.02 (t, J=4Hz, 2H), 3.04 (t, J=7.6Hz, 2H), 2.88 (s,
1H), 2.65 (m, 4H), 1.93 (s, 3H), 1.66 (m, 2H), 1.36 (m, 4H), 1.14 (t, J=7.5Hz, 3H), 0.91 (t, J
=6.9Hz, 3H).
5% is had respectively according to comparative example 1, the final liquid crystal material of the preparation process of comparative example 2 gained in background technique
Identical impurity generates, and reason is have 5% bromine coupling impurity to generate in first step coupling reaction process, and can be always present in rear
In the synthetic reaction in face, until final liquid crystal material.By being separated to final product column chromatographic purifying in background technique, collect miscellaneous
Matter, and nuclear magnetic spectrum detection is carried out to impurity, it is determined as first step bromine and is coupled introduced generation, the following institute of impurity nuclear magnetic spectrum
Show:
1H-NMR (400MHz, CDCl3) δ=7.69-7.64 (m, 1H), 7.56-7.47 (m, 4H), 7.47-7.37 (m,
2H), 7.32-7.26 (m, 2H), 6.94 (d, J=7.5Hz, 1H), 6.20 (dd, J=2.1,1.1Hz, 1H), 5.88 (dd, J=
2.2,1.1Hz, 1H), 4.47 (dt, J=14.7,7.3Hz, 4H), 3.74 (td, J=7.3,5.0Hz, 2H), 2.71-2.61 (m,
4H), 2.10 (td, J=7.4,1.0Hz, 2H), 2.02 (s, 3H), 1.97 (t, J=4.9Hz, 1H), 1.60 (tt, J=7.7,
5.5Hz, 2H), 1.30 (td, J=4.7,4.1,2.8Hz, 4H), 1.20 (t, J=8.0Hz, 3H), 0.94-0.86 (m, 3H).
Claims (10)
1. a kind of preparation method of liquid crystal material, which is characterized in that carry out as follows:
(1) using o ethyl aniline shown in formula I as starting material, upper bromine is protected to obtain acetylamino bromine shown in formula II through acetyl group
Benzene；
(2) acetylamino bromobenzene shown in formula II is coupled to obtain acetylamino biphenyl shown in formula III through a step Suzuki；
(3) acetylamino biphenyl shown in formula III obtains biphenyl halides shown in formula IV through halogen in deprotection, diazotising；
(4) biphenyl halides shown in formula IV react to obtain biphenylboronic acid shown in formula V with boron alkyl acid esters through n-BuLi lithiumation；
(5) using salicylaldhyde shown in formula VI as raw material, ether-containing shown in formula VII is obtained through upper bromine, Williamson etherification reaction
Bromobenzene；
(6) ether-containing bromobenzene shown in formula VII successively passes through Wittig reaction, hydroboration-oxidation reacts to obtain bromine containing alcohol ether shown in formula VIII
Benzene；
(7) biphenylboronic acid shown in bromobenzene containing alcohol ether and formula V shown in formula VIII obtains three shown in formula Ⅸ through a step Suzuki coupling reaction
Biphenylylmethylcarbinol；
(8) terphenyl ethyl alcohol and methacrylic chloride shown in formula Ⅸ obtain terphenyl acrylate shown in formula Ⅹ at ester；
(9) terphenyl acrylate shown in formula Ⅹ obtains final product liquid crystal material shown in formula Ⅺ through deprotection；
The structural formula of above-mentioned various shown compound is as follows:
Wherein, R is one of bromine Br or iodine I；
R1Selected from one of having structure group:
2. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (1) is will be shown in formula I
O ethyl aniline is dissolved in solvent A, and acetic anhydride is added at -5~20 DEG C, and TLC, which tracks to reaction, to be terminated, and reaction solution is cooled to -5
~20 DEG C, bromine and hydrogen peroxide is added, reacts 2~8h, TLC tracks to end of reaction, and aqueous solution of sodium bisulfite, reaction is added
Liquid obtains acetylamino bromobenzene shown in formula II through liquid separation, washing, concentration.
3. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (2) is by step (1)
Acetylamino bromobenzene shown in obtained formula II stirs after room temperature deaerates in solvent B under alkaline condition with to amyl phenyl boric acid
Palladium-containing catalyst is then added in 0.5~2h, then is placed in 60~120 DEG C of reactions 2~8h, TLC and tracks to end of reaction, reaction solution
It washed, be concentrated, obtain acetylamino biphenyl shown in formula III.
4. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (3) is by step (2)
Acetylamino biphenyl shown in obtained formula III is dissolved in solvent C, and 20wt%~60wt% aqueous sulfuric acid is added, is heated to reflux
0.5~4h stops heating and being cooled to -20~0 DEG C, sodium nitrite in aqueous solution is added dropwise；Bromination is added to another there-necked flask again
Cuprous, hydrobromic acid aqueous solution forms cuprous bromide-hydrobromic acid solution, and diazonium salt is added drop-wise to cuprous bromide-at 20~60 DEG C
In hydrobromic acid solution, 2~8h is reacted, TLC tracks to end of reaction, and reaction solution obtains formula IV through extraction, washing, drying, concentration
Shown biphenyl bromine；
Either, step (3) is that acetylamino biphenyl shown in formula III that step (2) obtains is dissolved in solvent C, and 10wt% is added
~30wt% aqueous hydrochloric acid solution or 20wt%~60wt% aqueous sulfuric acid are heated to reflux 0.5~4h, stop heating and cooling down
To -20~0 DEG C, sodium nitrite in aqueous solution is added dropwise；Potassium iodide aqueous solution is added to another there-necked flask again, at -20~30 DEG C
Diazonium salt is added drop-wise in potassium iodide aqueous solution, 2~8h is reacted, TLC tracks to end of reaction, reaction solution through extraction, washing, do
Dry, concentration, obtains biphenyl iodine shown in formula IV.
5. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (4) is by step (3)
Biphenyl halides shown in obtained formula IV are dissolved in solvent D, are stirred 0.5~2h through inert gas shielding, are cooled to -40~-80
DEG C be added dropwise lithium hexane solution, stir 0.5~2h after, instill boron alkyl acid esters, then be placed in -20~-80 DEG C reaction 2~
4h, TLC track to end of reaction, and aqueous hydrochloric acid solution hydrolysis is added at -20~30 DEG C, and reaction solution is obtained through liquid separation, washing, concentration
To biphenylboronic acid shown in formula V.
6. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (5) is by VI institute of formula
Showing that salicylaldhyde is dissolved in solvent E, bromine is added dropwise at -20~30 DEG C, reacts 2~8h, TLC tracks to end of reaction,
Then sodium sulfite is added and stirs 0.5~2h, after liquid separation, washing, drying, solvent F dissolution is added, organic bromine is then added
Compound R1- Br and alkali, through inert gas shielding, in 80~120 DEG C of 2~8h of return stirring, TLC, which tracks to reaction, to be terminated, reaction
Liquid through liquid separation, washing, drying, be concentrated to get ether-containing bromobenzene shown in formula VII, wherein R1For one of following groups:
7. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (6) is by step (5)
Ether-containing bromobenzene shown in obtained formula VII and methyl Wittig reagent under alkaline condition, in solvent G under inert gas protection,
In -20~150 DEG C of 2~8h of reaction, TLC, which tracks to reaction, to be terminated, and reaction solution is dissolved in solvent H after washing, drying, concentration,
Under inert gas protection, borane reagent is added dropwise at -40~30 DEG C, 40wt%~60wt% hydrogen-oxygen is added after reacting 1~3h
Change sodium water solution and 30wt% hydrogen peroxide, reacts 1~4h, TLC, which tracks to reaction, to be terminated, and through washing, drying, concentration, obtains formula
Bromobenzene containing alcohol ether shown in VIII.
8. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (7) is by step (4)
Bromobenzene containing alcohol ether shown in the formula VIII that biphenylboronic acid shown in obtained formula V and step (6) obtain is under alkaline condition in solvent I
Through room temperature deaerate protection stirring 0.5~2h, palladium-containing catalyst is then added, then be placed at 60~120 DEG C and react 2-8h, TLC with
Track to end of reaction, reaction solution is washed, is concentrated, and terphenyl ethyl alcohol shown in formula Ⅸ is obtained.
9. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (8) is by step (7)
Terphenyl ethyl alcohol shown in obtained formula Ⅸ is dissolved in solvent J, alkali is added, and deaerated and protected with inert gas, at -30~20 DEG C
Methacrylic chloride is added dropwise, natural 1~4h of temperature reaction, TLC track to end of reaction, reaction solution through liquid separation, washing, drying,
Concentration, obtains terphenyl acrylate shown in formula Ⅹ.
10. a kind of preparation method of liquid crystal material according to claim 1, it is characterised in that: step (9) is by step
(8) terphenyl acrylate shown in the formula Ⅹ obtained is dissolved in solvent K, and acidic materials are added drop-wise to reaction at -15~35 DEG C
Stirred in system, then at 25~30 DEG C react 2~6h, TLC track fully reacting after, reaction solution through liquid separation, washing, do
Dry, concentration, obtains final product liquid crystal material shown in formula Ⅺ.
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| CN109679666A (en) * | 2019-01-29 | 2019-04-26 | 武汉轻工大学 | Liquid-crystal compounds and preparation method thereof, liquid-crystal composition and microwave communication device |
| CN114522727A (en) * | 2022-03-09 | 2022-05-24 | 太原理工大学 | Halogenated aromatic linear conjugated polymer photocatalytic material, and preparation method and application thereof |
| CN114671745A (en) * | 2020-12-24 | 2022-06-28 | 江苏和成新材料有限公司 | Green method for synthesizing compound containing biaryl structure through Suzuki coupling reaction |
| CN114671744A (en) * | 2020-12-24 | 2022-06-28 | 江苏和成新材料有限公司 | Green method for synthesizing compound containing biaryl structure through Suzuki coupling reaction |
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| CN115636775A (en) * | 2021-07-20 | 2023-01-24 | 晶美晟光电材料（南京）有限公司 | Preparation method of sulfur-containing biphenyl liquid crystal compound |
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