CN1928002A - Liquid crystal compound 4'-cyclohexyloxy-4-diphenylcarboxylic acid-3-fluoro-4-cyanobenzene ester and preparation method thereof - Google Patents
Liquid crystal compound 4'-cyclohexyloxy-4-diphenylcarboxylic acid-3-fluoro-4-cyanobenzene ester and preparation method thereof Download PDFInfo
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- CN1928002A CN1928002A CN200610139018.5A CN200610139018A CN1928002A CN 1928002 A CN1928002 A CN 1928002A CN 200610139018 A CN200610139018 A CN 200610139018A CN 1928002 A CN1928002 A CN 1928002A
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Abstract
本发明涉及一种含氟原子和氰基的取代联苯羧酸酯类液晶化合物及其制备方法。该化合物的化学结构为4’－环己氧基－4－联苯羧酸－3－氟－4－氰基苯酯，其制备方法的特征为：通过Williamson醚化反应在对羟基联苯羧酸的4’－位上引入环己氧基，生成4’－环己氧基－4－联苯羧酸，再通过DCC脱水缩合，促使4’－环己氧基－4－联苯羧酸和2－氟－4－羟基苯腈缩合生成所需的化合物。本发明还涉及该化合物的用途，该单体液晶可以用于混配液晶中，而这种混配液晶可应用于液晶显示器中。The invention relates to a substituted biphenyl carboxylate liquid crystal compound containing fluorine atoms and cyano groups and a preparation method thereof. The chemical structure of the compound is 4'-cyclohexyloxy-4-biphenylcarboxylate-3-fluoro-4-cyanophenyl ester, and the preparation method is characterized in that: through the Williamson etherification reaction in p-hydroxybiphenylcarboxylate Introduce cyclohexyloxy group at the 4'-position of the acid to generate 4'-cyclohexyloxy-4-biphenylcarboxylic acid, and then dehydrate and condense 4'-cyclohexyloxy-4-biphenylcarboxylic acid through DCC Condensation with 2-fluoro-4-hydroxybenzonitrile produces the desired compound. The present invention also relates to the use of the compound. The monomer liquid crystal can be used in mixed liquid crystals, and the mixed liquid crystals can be used in liquid crystal displays.
Description
Technical field
The present invention relates to technical field of organic synthesis, especially relate to a kind of substituted biphenyl carboxylic acid esters liquid crystalline cpd and preparation method and purposes that contains 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 substituted biphenyl carboxylic acid esters liquid crystalline cpd that contains 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%～95%; Adding soluble alkali metal oxyhydroxide makes the potential of hydrogen of solution reach pH＞10, in solvent, add cyclohexane halide (so-called " halo " means that fluorine replaces, chlorine replaces, bromine replaces or iodine replaces) and parazon carboxylic acid, the ratio of both amount of substances is 2～5: 1, and the massfraction of parazon carboxylic acid in solution is 5%～30%.Under this condition, make both that condensation reaction take place.Temperature of reaction is 50～80 ℃.
2) after condensation reaction finishes, react, remove the by product that generates in the step 1), make 4 ' pure-cyclohexyloxy-4-biphenyl carboxylic acids by hydrolysis reaction with the ethanol-water mixed solvent solution of soluble alkali metal oxyhydroxide and the mixed solution of previous step reaction gained.The ratio of the amount of substance of employed parazon carboxylic acid is 2～5: 1 in used solubility oxyhydroxide and the step 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 '-cyclohexyloxy-4-biphenyl carboxylic acids and 2-fluoro-4-4-hydroxy-benzonitrile by dehydration condensation, generate target compound 4 '-cyclohexyloxy-4-biphenyl carboxylic acids-3-fluoro-4-cyanobenzene ester.The ratio of the amount of substance of DCC, 4 '-cyclohexyloxy-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) 0.02mol parazon carboxylic acid and 0.1mol potassium hydroxide are dissolved in 100ml 95% (volume fraction) ethanol, speed with about 1ml/min dropwise adds the 0.05mol bromocyclohexane, back flow reaction 108h, 70% (volume fraction) ethanolic soln meter 28ml that adds 0.1mol potassium hydroxide again continues backflow 2h.Add entry 100ml, concentrated hydrochloric acid 50ml, behind the heating 15min, cold filtration with distilled water wash, drying, with 95% (volume fraction) ethyl alcohol recrystallization, obtains 4 '-cyclohexyloxy-4-biphenyl carboxylic acids again, is the white plates crystal, productive rate 51%.
2) in there-necked flask, add 0.01mol 4 '-cyclohexyloxy-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 0.01mol 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 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 gets pure product 1.05g by column chromatography for separation, productive rate about 25%.
Implement 2
1) 0.05mol parazon carboxylic acid and 0.40mol potassium hydroxide are dissolved in 200ml 95% (volume fraction) ethanol, dropwise add 0.20mol iodocyclohexane, back flow reaction 120h with the speed of about 1ml/min.70% (volume fraction) ethanolic soln meter 40ml that adds 0.30mol potassium hydroxide afterwards continues backflow 2h.Add entry 200ml, concentrated hydrochloric acid 40ml mixes, and behind the heating 20min, cold filtration with distilled water wash, drying, with 95% (volume fraction) ethyl alcohol recrystallization, obtains 4 '-cyclohexyloxy-4-biphenyl carboxylic acids again, is the white plates crystal, productive rate 48%.
2) in there-necked flask, add 0.015mol 4 '-cyclohexyloxy-4-biphenyl carboxylic acids and 50ml anhydrous tetrahydro furan, after stirring is dissolved it fully, DCC (the N that adds 0.02mol, 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 gets pure product 1.42g by column chromatography for separation, productive rate about 23%.
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, 1601,1493cm
-1)
Carbonyl (3, C=O stretching vibration, 1739cm
-1)
Carbon oxygen singly-bound (4, C-O-C stretching vibration, 1255,1154cm
-1)
1H NMR (proton nmr spectra):
Proton 1: δ=7.07 * 10
-6, 2H
Proton 2,6: δ=7.73 * 10
-6, 3H
Proton 3: δ=7.88 * 10
-6, 2H
Proton 4: δ=8.19 * 10
-6, 2H
Proton 5: δ=7.46 * 10
-6, 1H
Proton 7: δ=8.07 * 10
-6, 1H
Proton 8: δ=1.38～2.51 * 10
-6, 10H
Proton 10: δ=4.43 * 10
-6, 1H
The structure of confirming institute's synthetic compound thus is consistent with expection.
The transformation behavior of finding institute's synthetic compound by differential calorimetric scanning analysis is:
K?100?N?256?I?252?N?69?K
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 100 ℃, 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 256 ℃, 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, white schlieren texture occurs at 252 ℃ earlier in the visual field, become crystal again 69 ℃ of crystallizations again.This explanation 4 '-cyclohexyloxy-4-biphenyl carboxylic acids-3-fluoro-4-cyanobenzene 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 '-cyclohexyloxy-4-biphenyl carboxylic acids-3-fluoro-4-cyanobenzene ester.
Claims (2)
1. a LCD compound---4 '-cyclohexyloxy-4-biphenyl carboxylic acids-3-fluoro-4-cyanobenzene ester, its structural formula is
2. a liquid crystalline cpd---the preparation method of 4 '-cyclohexyloxy-4-biphenyl carboxylic acids-3-fluoro-4-cyanobenzene ester is characterized in that
1) under the potential of hydrogen of pH＞10,50～80 ℃ temperature, in solution, add cyclohexane halide and parazon carboxylic acid, make both that condensation reaction take place, generate 4 '-cyclohexyloxy-4-biphenyl carboxylic acids,
2) after condensation finishes, under 50～80 ℃ of conditions, remove reactions steps 1 by hydrolysis reaction with the solution of highly basic in ethanol-water mixed solvent) in the by product that generates,
3) with N, the N-dicyclohexylcarbodiimide is a dewatering agent, and N, N-Dimethylamino pyridine are catalyzer, 0～30 ℃ of reaction down, impel 4 '-cyclohexyloxy-4-biphenyl carboxylic acids to become 4 '-cyclohexyloxy-4-biphenyl carboxylic acids-3-fluoro-4-cyanobenzene ester with 2-fluoro-4-4-hydroxy-benzonitrile dehydrating condensation.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113296310A (en) * | 2020-02-24 | 2021-08-24 | 广东普加福光电科技有限公司 | Quantum dot light conversion layer and preparation method thereof |
| CN116178685A (en) * | 2023-02-13 | 2023-05-30 | 宁夏清研高分子新材料有限公司 | A high-definition bright spot LCP material and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| USRE37270E1 (en) * | 1986-09-08 | 2001-07-10 | Merck Patent Gesellschaft | Liquid crystal phase |
| US5271865A (en) * | 1990-02-13 | 1993-12-21 | Merck Patent Gesellschaft Mit Beschrankter Haftung | Liquid-crystalline mixture of low viscosity |
| CN1315795C (en) * | 2005-06-08 | 2007-05-16 | 青岛科技大学 | Novel LCD compound p-phenyl-methoxy cinnamic acid -2-fluoro-4-hydroxy- benzonitrile ester and its preparation method |
| CN100368390C (en) * | 2006-01-06 | 2008-02-13 | 青岛科技大学 | Novel liquid crystal compound-4-(2-methyloxypropyl-1)-4-diphenyl carboxyl-2-fluoro-4-hydroxy benzonitrile ester, and its prepn. |
| CN1800154A (en) * | 2006-01-06 | 2006-07-12 | 青岛科技大学 | Novel liquid crystal compound 4'-(3-methylbutoxy-1)-4- diphenylcarboxylic acid-2-fluo-4-hydroxybenzenenitrile ester and its preparation method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113296310A (en) * | 2020-02-24 | 2021-08-24 | 广东普加福光电科技有限公司 | Quantum dot light conversion layer and preparation method thereof |
| CN116178685A (en) * | 2023-02-13 | 2023-05-30 | 宁夏清研高分子新材料有限公司 | A high-definition bright spot LCP material and its preparation method |
| CN116178685B (en) * | 2023-02-13 | 2025-06-06 | 宁夏清研高分子新材料有限公司 | A high-definition bright spot LCP material and preparation method thereof |
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