CN100368390C - Novel liquid crystal compound-4-(2-methyloxypropyl-1)-4-diphenyl carboxyl-2-fluoro-4-hydroxy benzonitrile ester, and its prepn. - Google Patents
Novel liquid crystal compound-4-(2-methyloxypropyl-1)-4-diphenyl carboxyl-2-fluoro-4-hydroxy benzonitrile ester, and its prepn. Download PDFInfo
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- CN100368390C CN100368390C CNB2006100421576A CN200610042157A CN100368390C CN 100368390 C CN100368390 C CN 100368390C CN B2006100421576 A CNB2006100421576 A CN B2006100421576A CN 200610042157 A CN200610042157 A CN 200610042157A CN 100368390 C CN100368390 C CN 100368390C
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- biphenyl carboxylic
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Abstract
The present invention relates to a substituted 4-biphenyl carboxylic acid ester liquid crystal compound containing fluorine atoms and cyano, and a preparation method thereof. The compound is in a chemical structure of 4'-(2-methylpropoxy-1)-4-biphenyl carboxylic acid-2-fluoro-4-hydroxyphenyl nitrile ester. The preparation method of the compound is characterized in that 2-methylpropoxy is introduced into a 4'-position of 4-biphenyl carboxylic acid to generate 4'-(2-methylpropoxy-1)-4-biphenyl carboxylic acid through a Williamson etherifying reaction, and then the 4'-(2-methylpropoxy-1)-4-biphenyl carboxylic acid and 2-fluoro-4-hydroxyphenyl nitrile are prompted to be condensed to generate the needed compound through DCC dehydrating condensation. The present invention also relates to the purposes of the compound. The monomer liquid crystal can be used in a mixed liquid crystal which can be applied to a liquid crystal displayer.
Description
Technical field
The present invention relates to technical field of organic synthesis, especially relate to a kind of preparation method and purposes that contains the replacement 4-biphenyl carboxylic acids class organic lcd compound of fluorine atom and cyano group.
Background technology
In recent years, liquid crystalline cpd and liquid crystal material become one of focus of applied chemistry and materials chemistry research, obtained widely using in each side such as electronics, optics, acoustics, biotechnology, chemical industry, and wherein the most extensive and the most important thing is its application aspect the electronics demonstration.Along with the development of information industry, to the requirement of liquid crystal material also in continuous raising.Though the report of relevant liquid crystal material aspect is existing a lot, but they all are not suitable in the display device, must satisfy requirements such as broad operating temperature range, lower operating voltage, low-viscosity, response fast, high stability because show the liquid crystal material of usefulness.
With 2-fluoro-4-4-hydroxy-benzonitrile is the advantage that the liquid crystalline cpd of intermediate has fluorinated liquid crystal and cyano group liquid crystal concurrently, be the important liquid crystalline cpd of a class that satisfies above-mentioned condition, represents the liquid crystal development trend, and therefore 2-fluoro-4-4-hydroxy-benzonitrile also become intermediate important in the liquid crystal chemical industry.This intermediate is at first the most synthetic by Japanese Sumitomo Chemical Co.Ltd. as far back as nineteen eighty-two, after this people use this intermediate to synthesize hundreds of liquid crystalline cpds, these compounds all have the advantage of high clearing point, wide liquid crystal working range, low-viscosity, are suitable as the moiety of the demonstration liquid crystal material of excellent property.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method who contains the substituted biphenyl carboxylic-acid liquid crystalline cpd of fluorine atom and cyano group, its structural formula is
This compound has the advantage that chemical property is stable, clearing point is high, liquid crystal range is wide, is the moiety of potential liquid crystal display material.
This compound is made by organic synthesis technology.The main points of the method for synthetic this compound are:
1) with the ethanol-water solution be mixed solvent, wherein the alcoholic acid volume percent is 70%～5%; Add soluble alkali metal oxyhydroxide and make the potential of hydrogen of solution reach pH＞10, (so-called " halo " means that the hydroxyl-massfraction of 4-biphenyl carboxylic acids in solution is 5%～30% to add 1-halo-2-methylpropane in solvent.Under this condition, make both that condensation reaction take place.Temperature of reaction is 50～80 ℃.
2) after condensation reaction finishes, react with the ethanol-water mixed solvent solution of soluble alkali metal oxyhydroxide and the mixed solution of previous step reaction gained, remove the by product that generates in the step 1) by hydrolysis reaction, make 4 ' pure-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids.The ratio of the amount of substance of employed 4 '-hydroxyl in used solubility oxyhydroxide and the step 1)-4-biphenyl carboxylic acids is 2～5: 1, the pH of reaction system＞12, and temperature of reaction is 50～80 ℃, the alcoholic acid volume percent is 60%～80% in the mixed solvent.
3) with DCC (N, the N-dicyclohexylcarbodiimide) is dewatering agent, DMAP (N, the N-Dimethylamino pyridine) is catalyzer, anhydrous tetrahydro furan is a solvent, impel 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids and 2-fluoro-4-4-hydroxy-benzonitrile by dehydration condensation, generate target compound 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids-2-fluorine .4-4-hydroxy-benzonitrile ester.The ratio of the amount of substance of DCC, 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids, 2-fluoro-4-4-hydroxy-benzonitrile, DMAP is 1～1.5: 1～2: 1: 0.01～0.02, and the initial mass mark of 2-fluoro-4-4-hydroxy-benzonitrile in solution is 5%～20%.Temperature of reaction is 0～30 ℃.
To help to understand the present invention by following experiment, but following experiment does not limit content of the present invention.
Implement 1
1) 0.01mol 4 '-hydroxyl-4-biphenyl carboxylic acids and 0.02mol potassium hydroxide are dissolved in 40ml95% (volume fraction) ethanol, speed with about 1ml/min dropwise adds 0.03mol 1-bromo-2-methylpropane again, back flow reaction 24h, 70% (volume fraction) ethanolic soln meter 14ml that adds 0.02mol potassium hydroxide again continues backflow 2h.Add entry 100ml, concentrated hydrochloric acid 20ml, behind the heating 15min, cold filtration with distilled water wash, drying, again with 95% (volume fraction) ethyl alcohol recrystallization, obtains 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids, is the white plates crystal, productive rate 54%.
2) in there-necked flask, add 0.01mol 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids and 20ml anhydrous tetrahydro furan, after stirring is dissolved it fully, DCC (the N that adds 0.01mol, the N-dicyclohexylcarbodiimide), after waiting to become turbid, with 0.01mol2-fluoro-4-4-hydroxy-benzonitrile and a small amount of DMAP[4-(N, the N-dimethylamino) pyridine] be dissolved in wiring solution-forming in the 20ml anhydrous tetrahydro furan, slowly splash in the flask, about 10 ℃, stir 24h, after reaction finishes, remove by filter by product N, the N-dicyclohexylurea (DCU), adding distil water is precipitated out product in filtrate, dry back is by the pure product 0.58g of column chromatography for separation, productive rate about 15%.
Implement 2
1) 0.02mol 4 '-hydroxyl-4-biphenyl carboxylic acids and 0.05mol potassium hydroxide are dissolved in 100ml95% (volume fraction) ethanol, add 0.03mol 1-iodo-2-methylpropane again, back flow reaction 48h.70% (volume fraction) ethanolic soln meter 35ml that adds 0.03mol potassium hydroxide afterwards continues backflow 2h.Add entry 100ml, concentrated hydrochloric acid 40ml mixes, behind the heating 20min, cold filtration is with distilled water wash, drying, again with 95% (volume fraction) ethyl alcohol recrystallization, obtain 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids, be the white plates crystal, productive rate 49%.
2) in there-necked flask, add 0.015mol 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids and 50ml anhydrous tetrahydro furan, after stirring is dissolved it fully, DCC (the N that adds 0.01mol, the N-dicyclohexylcarbodiimide), after waiting to become turbid, with 0.015mol 2-fluoro-4-4-hydroxy-benzonitrile and a small amount of DMAP[4-(N, the N-dimethylamino) pyridine] be dissolved in wiring solution-forming in the 35ml anhydrous tetrahydro furan fully, slowly splash in the flask, about 20 ℃, stir 24h, after reaction finishes, remove by filter by product N, the N-dicyclohexylurea (DCU), adding distil water is precipitated out product in filtrate, dry back is by the pure product 0.9g of column chromatography for separation, productive rate about 17%.
By IR,
1H NMR method characterizes institute's synthetic compound, to confirm its structure.
IR (infrared spectra):
Cyano group (1, the stretching vibration of C ≡ N key, 2235cm
-1)
Phenyl ring (2, the stretching vibration of phenyl ring carbon skeleton, 1602,1580,1528cm
-1)
Carbonyl (3, C=O stretching vibration, 1743cm
-1)
Carbon oxygen singly-bound (4, C-O-C stretching vibration, 1250,1143cm
-1)
1HNMR (proton nmr spectra):
Proton 1: δ=7.08 * 10
-6, s=2.03
Proton 2: δ=7.74 * 10
-6, s=3.20 (overlapping)
Proton 3: δ=7.89 * 10
-6, s=2.12
Proton 4: δ=8.17 * 10
-6, s=2.02
Proton 5: δ=7.47 * 10
-6, s=1.0
Proton 6: δ=7.74 * 10
-6, s=3.20 (overlapping)
Proton 7: δ=8.10 * 10
-6, s=0.98
Proton 8: δ=1.00 * 10
-6, s=5.90
Proton 9: δ=2.04 * 10
-6, s=1.05
Proton 10: δ=3.81 * 10
-6, s=2.07
The structure of confirming institute's synthetic compound thus is consistent with expection.
By DSC (differential calorimetric scanning) and POM (orthogonal polarizing microscope) the liquid crystal phase transition character of institute's synthetic compound is characterized.
The transformation behavior of finding institute's synthetic compound by differential calorimetric scanning analysis is:
K?131.8N?186.3I?185.3N?106.5K
The transformation behavior that meets thermotropic liquid crystal.
By orthogonal polarizing microscope institute's synthetic sample is observed, sample presents tabular crystal under the normal temperature under polarizing microscope, with the speed heating of sample with 5 ℃/min, the sample fusion enters liquid crystal state during to about 132 ℃, occurs a large amount of drops in the visual field, occurs numerous blackstreaks in the drop, the cross frosting phenomenon appears in infall, present typical striped texture, and flow rapidly, show that sample exists with nematic phase at present.Reheat to 188 ℃, schlieren texture reduce rapidly to disappear, and the visual field presents a slice black, shows that sample has been converted into isotropic liquid.During cooling, earlier at 186 ℃ of schlieren textures that yellow background occurs, become crystal again 108 ℃ of crystallizations again in the visual field.This explanation 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids-2-fluoro-4-4-hydroxy-benzonitrile ester is a kind of change thermotropic liquid crystal.
More than be suitable as the ideal moiety of liquid crystal composite used in the liquid-crystal display, be suitable in the used liquid crystal composite material of liquid-crystal displays such as TN, STN, TFT about the test result of liquid crystal property explanation 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids-2-fluoro-4-4-hydroxy-benzonitrile ester.
Claims (1)
1. the liquid crystalline cpd that structural formula is formula (1)---the preparation method of 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids-2-fluoro-4-4-hydroxy-benzonitrile ester is characterized in that
1) under the potential of hydrogen of pH＞10,50～80 ℃ temperature, in solvent, add 1-halo-2-methylpropane and 4 '-hydroxyl-4-biphenyl carboxylic acids, make both that condensation reaction take place, generate 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids, so-called " halo " means that fluorine replaces, chlorine replaces, bromine replaces or iodine replaces;
2) after condensation finishes, under 50～80 ℃ of conditions, remove reactions steps 1 by hydrolysis reaction with the solution of soluble alkali metal oxyhydroxide in ethanol-water mixed solvent) in the by product that generates;
3) with N, the N-dicyclohexylcarbodiimide is a dewatering agent, N, the N-Dimethylamino pyridine is a catalyzer, 0～30 ℃ of reaction down, impel 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids to become 4 '-(2-methyl-prop Oxy-1)-4-biphenyl carboxylic acids-2-fluoro-4-4-hydroxy-benzonitrile ester with 2-fluoro-4-4-hydroxy-benzonitrile dehydrating condensation.
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| CNB2006100421576A CN100368390C (en) | 2006-01-06 | 2006-01-06 | Novel liquid crystal compound-4-(2-methyloxypropyl-1)-4-diphenyl carboxyl-2-fluoro-4-hydroxy benzonitrile ester, and its prepn. |
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| CNB2006100421576A CN100368390C (en) | 2006-01-06 | 2006-01-06 | Novel liquid crystal compound-4-(2-methyloxypropyl-1)-4-diphenyl carboxyl-2-fluoro-4-hydroxy benzonitrile ester, and its prepn. |
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| CN100368390C true CN100368390C (en) | 2008-02-13 |
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| CN100412159C (en) * | 2006-09-21 | 2008-08-20 | 青岛科技大学 | Liquid crystal compound 4'-cyclohexyloxy-4-diphenylcarboxylic acid-3-fluoro-4-cyanobenzene ester and preparation method thereof |
| CN107831622B (en) * | 2017-11-23 | 2020-05-22 | 湖南宏晶电子有限公司 | LCD liquid crystal display device |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4886621A (en) * | 1986-09-08 | 1989-12-12 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid crystal phase |
| US5271865A (en) * | 1990-02-13 | 1993-12-21 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid-crystalline mixture of low viscosity |
| US6849309B2 (en) * | 1994-03-17 | 2005-02-01 | Hitachi, Ltd. | Active matrix type liquid crystal display apparatus |
| CN1626617A (en) * | 2003-11-06 | 2005-06-15 | 默克专利股份有限公司 | Liquid-crystal medium and electro-optical display containing same |
-
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- 2006-01-06 CN CNB2006100421576A patent/CN100368390C/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4886621A (en) * | 1986-09-08 | 1989-12-12 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid crystal phase |
| US5271865A (en) * | 1990-02-13 | 1993-12-21 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid-crystalline mixture of low viscosity |
| US6849309B2 (en) * | 1994-03-17 | 2005-02-01 | Hitachi, Ltd. | Active matrix type liquid crystal display apparatus |
| CN1626617A (en) * | 2003-11-06 | 2005-06-15 | 默克专利股份有限公司 | Liquid-crystal medium and electro-optical display containing same |
Non-Patent Citations (2)
| Title |
|---|
| (S)-2-甲基丁氧基氟代联苯甲酸苯酯类液晶化合物的合成及其性能研究. 荣国斌，马汝建.液晶与显示，第12卷第3期. 1997 * |
| 手性液晶的研究. 陈其超，李国镇.华东理工大学学报，第20卷第3期. 1994 * |
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