CN101225026B - Fluorine substituted-4,4'-biphenyl diphenol diiallyl ether synthetic method - Google Patents
Fluorine substituted-4,4'-biphenyl diphenol diiallyl ether synthetic method Download PDFInfo
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- CN101225026B CN101225026B CN2008100140656A CN200810014065A CN101225026B CN 101225026 B CN101225026 B CN 101225026B CN 2008100140656 A CN2008100140656 A CN 2008100140656A CN 200810014065 A CN200810014065 A CN 200810014065A CN 101225026 B CN101225026 B CN 101225026B
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Abstract
The invention relates to a synthesis method of fluoro-4, 4'- biphenyl diphenol di-allylic ether used as liquid crystal material, comprising steps as follows: under the effects of the palladium catalysts and ligands, cross-coupling reaction is carried out for the fluoro-p-bromoanisole and (fluoro) p-methoxybenzeneboronic acid to generate fluoro-4, 4'-dimethoxy-biphenyl; with the HI, hydroxylation reaction is carried out to generate fluoro-4, 4'- biphenyl diphenol; etherification reaction is carried out to generate fluoro-4, 4'- biphenyl diphenol di-allylic ether. The synthesized products serving as the liquid crystalline monomer are applied in preparing liquid crystal mixtures as well as in synthesizing the liquid crystalline polymer to manufacture a plurality of electronic films. The synthesis method of fluoro-4, 4'- biphenyl diphenol di-allylic ether used as liquid crystal material has the advantages of simple operation, mild reaction conditions, low production cost, and suitability to the industrial production.
Description
Technical field
The present invention relates to a class fluoro-4, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether belongs to organic chemistry liquid crystal material manufacturing technology field.
Background technology
The Flat Panel Display Industry fast development of taking as the leading factor with TFT-LCD has in recent years brought revolutionary variation for people's live and work, makes that also the liquid crystal industry competition is more and more fierce.The investigator constantly develops new electronic material to satisfy growing industry requirement.
The liquid crystal material that contains carbon-carbon double bond is widely used recently.Add the monomer liquid crystal that contains carbon-carbon double bond in mixed liquid crystal, the elastic constant that not only can improve liquid crystal is with the reduction rotary viscosity, thus the raising response speed; Can also improve liquid crystal viscosity under the low temperature to enlarge the use temperature scope.
The liquid crystal material that contains carbon-carbon double bond is the monomer of synthetic liquid crystalline polymers, and the macromolecular material that contains liquid crystalline polymers all is widely used in every field, especially in the flat pannel display industry.In the material of decision liquid-crystal display qualities such as polaroid, compensate film, oriented material, the liquid crystal monomer that contains unsaturated carbon-carbon double bond is crucial component.Synthetic different polymerisable monomer liquid crystal is developed various liquid crystalline polymerss and various application, is to show emerging field of industry.
Fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether are the very promising monomer liquid crystal materials of a class, and it also can be used as polymer monomer simultaneously, is used to prepare the high molecule liquid crystal polymkeric substance.We have synthesized fluoro-4 first, 4 '-'-biphenyl diphenol dual-allyl ether, and thinking has good application prospects in the demonstration field.
Summary of the invention
In view of the foregoing, the invention provides a kind of synthetic method each the step all have selectivity and productive rate preferably, and simple to operate, reaction conditions is gentle, the fluoro of low production cost-4, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether.
Fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether, its chemical structural formula is as follows:
W=F、H;X=F、H;Y=F、H;Z=F、H
And have at least one to be fluorine atom among W, X, Y, the Z.
Fluoro-4, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether, step is as follows:
At first, fluoro para-bromoanisole and fluoro,, carry out cross-coupling reaction and generate fluoro-4,4 '-dimethoxy-biphenyl under the alkali acting in conjunction at palladium class catalyzer, part methoxyphenylboronic acid in appropriate solvent; Under the HI effect, generate fluoro-4,4 '-'-biphenyl diphenol in carrying out hydroxylating in the Glacial acetic acid then; Last and chlorallylene carries out etherification reaction and generates fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether in dehydrated alcohol.
In one step of linked reaction, fluoro is 1.0~2.0: 1 to the mol ratio of methoxyphenylboronic acid and fluoro para-bromoanisole, preferred 1.2~1.5: 1.
In one step of linked reaction, palladium class catalyzer can be selected PdCl for use
2, Pd (NO
3)
2, Pd (0AC)
2Deng palladium salt, wherein preferred PdCl
2The part of catalyzer can be selected tricyclohexyl phosphine, tri-butyl phosphine, two diamantane normal-butyl phosphines, biphenyl dicyclohexyl phosphine etc. for use, wherein preferred tricyclohexyl phosphine.
In one step of linked reaction, alkali can be selected K for use
2CO
3, KOH, K
3PO
4, KF etc., wherein preferred K
2CO
3
In one step of linked reaction, reaction solvent can be selected the mixed solvent of THF, DMF, DMAC and water for use, the mixed solvent of wherein preferred THF and water.
In one step of linked reaction, temperature of reaction is 60~110 ℃, preferred 60~70 ℃; Reaction times is 3~8 hours, preferred 4~5 hours.
In one step of hydroxylating, HI (45%) and fluoro-4, the mol ratio of 4 '-dimethoxy-biphenyl is 4.0~10.0: 1, preferred 5.0~7.0: 1.
In one step of hydroxylating, temperature of reaction is 90~120 ℃, preferred 100~110 ℃; Reaction times is 6~12 hours, preferred 8~10 hours.
In one step of etherification reaction, chlorallylene and fluoro-4, the mol ratio of 4 '-'-biphenyl diphenol is 3.0~6.0: 1, preferred 4.0~5.0: 1.
In one step of etherification reaction, temperature of reaction is 40~70 ℃, preferred 40~50 ℃; Reaction times is 4~10 hours, preferred 6~8 hours.
In one step of etherification reaction, need to add the HBr that appropriate bases generates with neutralization, thereby promote reaction to carry out, the alkali of adding can be selected KOH, K for use
2CO
3, K
3PO
4Deng, preferred KOH.
Above-mentioned linked reaction, hydroxylating, etherification reaction, the reaction formula in each step is as follows:
Fluoro of the present invention-4, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether, each the step all has selectivity and productive rate preferably, and simple to operate, reaction conditions is gentle, low production cost, quality product is better, aspect liquid crystal material good application prospects is arranged.
Embodiment
For the present invention is described better, after specific embodiment is described in, but the present invention is not limited in following example.
Fluoro of the present invention-4, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether, step is as follows:
(1), fluoro is to methoxyphenylboronic acid and fluoro para-bromoanisole (1.2~1.5) in molar ratio: 1 feeds intake, at catalyst P dCl
2, part tricyclohexyl phosphine, K
2CO
3Under the acting in conjunction, refluxed 4~5 hours in 60~70 ℃ in the THF-water medium, reaction finishes after extraction, washing, recrystallization obtain fluoro-4,4 '-dimethoxy-biphenyl;
(2), HI (45%) and the above-mentioned fluoro that obtains-4,4 '-dimethoxy-biphenyl is (5.0~7.0) in molar ratio: 1 feeds intake, in the Glacial acetic acid medium, refluxed 8~10 hours in 100~110 ℃, after reaction finishes after filtration, washing obtains fluoro-4,4 '-'-biphenyl diphenol;
(3), chlorallylene and the above-mentioned fluoro that obtains-4,4 '-'-biphenyl diphenol is (4.0~5.0) in molar ratio: 1 feeds intake, in the presence of KOH, reacted 6~8 hours in 40~50 ℃ in the anhydrous ethanol medium, reaction finishes after recrystallization, cross post, oven dry obtains the finished product fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether.
Embodiment 1
In the 250mL there-necked flask, add the adjacent fluorine para-bromoanisole of 10.3g (0.050moL) successively, 10.2g (0.060moL) adjacent fluorine is to methoxyphenylboronic acid, 10.3g (0.075moL) salt of wormwood, 3.3mg (2.5E-5moL) Palladous chloride, 14.0mg (5E-5moL) tricyclohexyl phosphine, 50mL water, 50mL THF.Mechanical stirring, spherical condensation tube, temperature are installed on there-necked flask to be taken into account nitrogen conduit, and there-necked flask is placed oil bath.Start and stir and heating, temperature refluxed 4~5 hours for 60~70 ℃ in being warming up to.Be cooled to below 50 ℃, add 100mL toluene, stirred 5 minutes, change the 500mL separating funnel over to, upper organic phase is told in layering, and lower floor's water merges organic phase with the extraction of 100mL toluene.Take off most solvent and get Off-white solid 10g.With 15mL ethyl acetate, 10mL sherwood oil recrystallization, filter is done, and gets oyster white crystal 10g.GC:99.5%, yield: 81.0%.
Embodiment 2
With a fluorine para-bromoanisole, adjacent fluorine is a raw material to methoxyphenylboronic acid, according to obtaining 2,2 '-two fluoro-4,4 '-dimethoxy-biphenyl with embodiment 1 similar methods.GC:99.7%, yield: 83.0%.
Embodiment 3
With 2,3-difluoro para-bromoanisole is to the outer raw material of methoxyphenylboronic acid, according to obtaining 2 with embodiment 1 similar methods, 3-two fluoro-4,4 '-dimethoxy-biphenyl.GC:99.6%, yield: 86.0%.
Embodiment 4
With 2,3-difluoro para-bromoanisole, adjacent fluorine is a raw material to methoxyphenylboronic acid, according to obtaining 2,3,2 '-three fluoro-4,4 '-dimethoxy-biphenyl with embodiment 1 similar methods.GC:99.6%, yield: 78.5%.
Embodiment 5
With 2,3-difluoro para-bromoanisole, a fluorine is a raw material to methoxyphenylboronic acid, according to obtaining 2,3,3 '-three fluoro-4,4 '-dimethoxy-biphenyl with embodiment 1 similar methods.GC:99.4%, yield: 79.0%.
Embodiment 6
In the 1L there-necked flask, add 25.0g (0.1moL) 2,3 '-two fluoro-4 successively, 4 '-dimethoxy-biphenyl, 140.0g (0.5moL) the 45%HI aqueous solution, 300mL Glacial acetic acid.Mechanical stirring, spherical condensation tube and thermometer are installed on there-necked flask, and there-necked flask is placed oil bath.Start and stir and heating, temperature refluxed 8~10 hours for 100~110 ℃ in being warming up to.Be cooled to 20~25 ℃ of filtrations, filter cake is used 50mL * abundant drip washing of 3 ethylene dichloride then to be washed to neutrality.In 100~110 ℃, vacuum-drying 8~10 hours gets Off-white solid powder 38g.GC:99.6%, yield: 85.5%.
Embodiment 7
With 2,2 '-two fluoro-4,4 '-dimethoxy-biphenyl are raw material, according to obtaining 2,2 '-two fluoro-4,4 '-'-biphenyl diphenol with embodiment 6 similar methods.GC:99.8%, yield: 84.0%.
Embodiment 8
With 2,3-two fluoro-4,4 '-dimethoxy-biphenyl is a raw material, according to obtaining 2 with embodiment 6 similar methods, 3-two fluoro-4,4 '-'-biphenyl diphenol.GC:99.7%, yield: 80.0%.
Embodiment 9
With 2,3,2 '-three fluoro-4,4 '-dimethoxy-biphenyl are raw material, according to obtaining 2,3,2 '-three fluoro-4,4 '-'-biphenyl diphenol with embodiment 6 similar methods.GC:99.3%, yield: 81.5%.
Embodiment 10
2,3,3 '-three fluoro-4,4 '-'-biphenyl diphenol
Synthetic
With 2,3,3 '-three fluoro-4,4 '-dimethoxy-biphenyl are raw material, according to obtaining 2,3,3 '-three fluoro-4,4 '-'-biphenyl diphenol with embodiment 6 similar methods.GC:99.4%, yield: 82.0%.
Embodiment 11
In the 250mL there-necked flask, add 22.2g (0.10moL) 2 successively, 3 '-two fluoro-4,4 '-'-biphenyl diphenol, 13.5g (0.24moL) KOH, the 75mL dehydrated alcohol,, fluid-tight, mechanical stirring, spherical condensation tube, constant pressure funnel and thermometer are installed on there-necked flask, and there-necked flask are placed oil bath.Start and stir and heating, be warming up to 40~50 ℃ of interior temperature, drip 38.3g (0.50moL) chlorallylene from constant pressure funnel in system, temperature finishes for about 20 minutes at 40~50 ℃ in controlling in the dropping process.40~50 ℃ of slow back flow reaction of temperature are 6~8 hours in continuing at, be cooled to 15~20 ℃ of filtrations, filter cake is with the abundant drip washing of 30mL * 3 time dehydrated alcohol, get pale yellow crystals 30g, solid is dissolved in 300mL toluene, crosses the neutral alumina post, and with the drip washing of 200mL toluene, take off most solvent, get white crystal 25g.GC:99.6%, yield: 83.0%, mp:81.3~82.8 ℃.
Embodiment 12
With 2,2 '-two fluoro-4,4 '-'-biphenyl diphenol are raw material, according to obtaining 2,2 '-two fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether with embodiment 11 similar methods.GC:99.7%, yield: 81.5%.
Embodiment 13
With 2,3-two fluoro-4,4 '-'-biphenyl diphenol is a raw material, according to obtaining 2 with embodiment 11 similar methods, 3-two fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether.GC:99.5%, yield: 82.0%, mp:65.0~66.3 ℃.
Embodiment 14
With 2,3,2 '-three fluoro-4,4 '-'-biphenyl diphenol are raw material, according to obtaining 2,3,2 '-three fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether with embodiment 11 similar methods.GC:99.1%, yield: 78.5%, mp:55.6~56.9 ℃.
Embodiment 15
With 2,3,3 '-three fluoro-4,4 '-'-biphenyl diphenol are raw material, according to obtaining 2,3,3 '-three fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether with embodiment 11 similar methods.GC:99.2%, yield: 79.0%.mp:54.7~56.1℃。
Claims (9)
1. fluoro-4, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether, its chemical structural formula is as follows:
W=F、H;X=F、H;Y=F、H;Z=F、H
And have at least one to be fluorine atom among W, X, Y, the Z;
It is characterized in that step is as follows:
Fluoro para-bromoanisole and fluoro to methoxyphenylboronic acid at palladium class catalyzer, part, under the alkali acting in conjunction, in appropriate solvent, carry out cross-coupling reaction and generate fluoro-4,4 '-dimethoxy-biphenyl, under the HI effect, carry out hydroxylating in the Glacial acetic acid and generate fluoro-4,4 '-'-biphenyl diphenol then, last and chlorallylene carries out etherification reaction and generates fluoro-4,4 '-'-biphenyl diphenol dual-allyl ether in dehydrated alcohol.
2. fluoro-4 according to claim 1, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether is characterized in that, and in one step of linked reaction, fluoro is 1.0~2.0: 1 to the mol ratio of methoxyphenylboronic acid and fluoro para-bromoanisole, and palladium class catalyzer is PdCl
2, Pd (NO
3)
2, Pd (OAC)
2In a kind of, the part of catalyzer is a kind of in tricyclohexyl phosphine, tri-butyl phosphine, two diamantane normal-butyl phosphines, the biphenyl dicyclohexyl phosphine, alkali is K
2CO
3, KOH, K
3PO
4, a kind of among the KF, reaction solvent is the mixed solvent of a kind of and water among THF, DMF, the DMAC.
3. fluoro-4 according to claim 2, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether is characterized in that, and in one step of linked reaction, fluoro is 1.2~1.5: 1 to the mol ratio of methoxyphenylboronic acid and fluoro para-bromoanisole, and palladium class catalyzer is PdCl
2, the part of catalyzer is a tricyclohexyl phosphine, alkali is K
2CO
3, reaction solvent is the mixed solvent of THF and water.
4. fluoro-4 according to claim 1, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether is characterized in that, and in one step of linked reaction, temperature of reaction is 60~110 ℃, and the reaction times is 3~8 hours.
5. fluoro-4 according to claim 4, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether is characterized in that, in one step of linked reaction, temperature of reaction is 60~70 ℃; Reaction times is 4~5 hours.
6. fluoro-4 according to claim 1, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether, it is characterized in that, in one step of hydroxylating, 45%HI and fluoro-4, the mol ratio of 4 '-dimethoxy-biphenyl is 4.0~10.0: 1, and temperature of reaction is 90~120 ℃, and the reaction times is 6~12 hours.
7. fluoro-4 according to claim 6, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether, it is characterized in that, in one step of hydroxylating, 45%HI and fluoro-4, the mol ratio of 4 '-dimethoxy-biphenyl is 5.0~7.0: 1, and temperature of reaction is 100~110 ℃, and the reaction times is 8~10 hours.
8. fluoro-4 according to claim 1, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether, it is characterized in that, in one step of etherification reaction, chlorallylene and fluoro-4, the mol ratio of 4 '-'-biphenyl diphenol is 3.0~6.0: 1, temperature of reaction is 40~70 ℃, reaction times is 4~10 hours, needs to add the HBr that appropriate bases generates with neutralization, and the alkali of adding is KOH, K
2CO
3, K
3PO
4In a kind of.
9. fluoro-4 according to claim 8, the synthetic method of 4 '-'-biphenyl diphenol dual-allyl ether, it is characterized in that, in one step of etherification reaction, chlorallylene and fluoro-4, the mol ratio of 4 '-'-biphenyl diphenol is 4.0~5.0: 1, temperature of reaction is 40~50 ℃, reaction times is 6~8 hours, needs to add the HBr that appropriate bases generates with neutralization, and the alkali of adding is KOH.
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CN102131897A (en) * | 2008-09-01 | 2011-07-20 | 智索株式会社 | Liquid crystal composition and liquid crystal display element |
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JP5494486B2 (en) * | 2008-09-22 | 2014-05-14 | Jnc石油化学株式会社 | Liquid crystal composition and liquid crystal display element |
JP5765227B2 (en) * | 2009-10-01 | 2015-08-19 | Jnc株式会社 | Liquid crystalline compound having negative dielectric anisotropy, liquid crystal composition using the same, and liquid crystal display device |
CN102211984B (en) * | 2011-03-28 | 2013-10-30 | 中国科学院化学研究所 | Epoxy molding compound, epoxy resin and preparation methods thereof |
CN102336635B (en) * | 2011-07-12 | 2014-03-12 | 中国科学院化学研究所 | Epoxy resin and preparation method and application thereof |
CN108485683B (en) * | 2018-05-21 | 2020-04-28 | 中节能万润股份有限公司 | Liquid crystal aligning agent, liquid crystal alignment film and liquid crystal display element |
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