CN1315795C - Novel LCD compound p-phenyl-methoxy cinnamic acid -2-fluoro-4-hydroxy- benzonitrile ester and its preparation method - Google Patents
Novel LCD compound p-phenyl-methoxy cinnamic acid -2-fluoro-4-hydroxy- benzonitrile ester and its preparation method Download PDFInfo
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- CN1315795C CN1315795C CNB2005100437118A CN200510043711A CN1315795C CN 1315795 C CN1315795 C CN 1315795C CN B2005100437118 A CNB2005100437118 A CN B2005100437118A CN 200510043711 A CN200510043711 A CN 200510043711A CN 1315795 C CN1315795 C CN 1315795C
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- styracin
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Abstract
本发明涉及一种含氟氰基肉桂酸酯类液晶化合物及其制备方法。该化合物的结构式如图所示。其制备方法的特征为：通过Williamson醚化反应在肉桂酸(3-苯基丙烯酸)的4-位上引入烷氧基，再通过DCC脱水缩合，促使取代肉桂酸和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，该化合物可以用于混配液晶中，还可应用于各类液晶显示器中。The invention relates to a fluorine-containing cyanocinnamate liquid crystal compound and a preparation method thereof. The structural formula of this compound is shown in the figure. Its preparation method is characterized by: introducing an alkoxy group at the 4-position of cinnamic acid (3-phenylacrylic acid) through Williamson etherification reaction, and then dehydrating and condensing through DCC to promote the substitution of cinnamic acid and 2-fluoro-4-hydroxyl Benzonitrile is condensed to give the desired compound. The present invention also relates to the use of the compound, which can be used in compounding liquid crystals and various liquid crystal displays.
Description
Technical field
The present invention relates to technical field of organic synthesis, especially relate to a kind of cinnamate derivative organic lcd compound that contains fluorine atom and cyano group-benzyloxy styracin-2-fluoro-4-4-hydroxy-benzonitrile ester and its production and use.
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, and these compounds all have low viscosity, low electrical conductivity, excellent in chemical and optical stability.These compounds have been widely used in field of electronic display at present.
Summary of the invention
The purpose of this invention is to provide a kind of new cinnamate derivative liquid crystalline cpd that contains fluorine, cyano group, premium properties fluorine-containing, cyano group liquid crystal type compound is further brought into play, be widely used in the liquid crystal that is mixed under the different situations.The present invention is as follows to benzyloxy styracin-2-fluoro-4-4-hydroxy-benzonitrile ester chemical structural formula:
The present invention has advantages such as chemical property is stable, clearing point is high, liquid crystal range is wide, is the good composition of forming liquid crystal display material.
The present invention is by methodology of organic synthesis system, and its synthetic method main points are as follows:
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 halogenation benzyl (halogen atom comprises fluorine, chlorine, bromine atoms) and p-Coumaric Acid, the ratio of both amount of substances is 2～5: 1, and the massfraction of p-Coumaric 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 pure the benzyloxy styracin by hydrolysis reaction with the ethanol-water mixed solvent solution of soluble alkali metal oxyhydroxide mixed solution with previous step reaction gained.The ratio of the amount of substance of employed p-Coumaric 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 benzyloxy styracin and 2-fluoro-4-4-hydroxy-benzonitrile are passed through dehydration condensation, generate target compound benzyloxy styracin-2-fluoro-4-4-hydroxy-benzonitrile ester.DCC, be 1～1.5: 1～2 to the ratio of the amount of substance of benzyloxy styracin, 2-fluoro-4-4-hydroxy-benzonitrile, DMAP: 1: 0.01～0.02, 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 p-Coumaric Acid and 0.02mol potassium hydroxide are dissolved in 40ml 95% (volume fraction) ethanol, speed with about 1ml/min dropwise adds the 0.03mol cylite 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, with 95% (volume fraction) ethyl alcohol recrystallization, obtains the benzyloxy styracin again, is the white plates crystal, productive rate 54%.
2) in there-necked flask, add 0.01mol to benzyloxy styracin 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, go out pure product 0.59g by column chromatography for separation after drying, productive rate about 16%.
Implement 2
1. 0.02mol p-Coumaric Acid and 0.05mol potassium hydroxide are dissolved in 100ml 95% ethanol, add the 0.03mol toluene bromide again, back flow reaction, and with the progress that the tlc check is reacted, disappear until raw material.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, and behind the heating 20min, cold filtration with distilled water wash, drying, again with 95% ethyl alcohol recrystallization, obtains 4-benzyloxy styracin, is the white plates crystal, productive rate 49%.
2. in there-necked flask, add 0.015mol 4-to benzyloxy styracin 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) adds distilled water product is precipitated out in filtrate, go out pure product 0.89g by column chromatography for separation after drying, productive rate about 17%.
By IR,
1The HNMR method characterizes above embodiment institute synthetic compound, to confirm its structure.
IR (infrared spectra):
Cyano group (1, the stretching vibration of C ≡ N key, 2236cm
-1)
Phenyl ring (2, the stretching vibration of phenyl ring carbon skeleton, 1603,1577,1510cm
-1)
Carbonyl (3, C=O stretching vibration, 1711cm
-1)
Carbon oxygen singly-bound (4, C-O-C stretching vibration, 1232,1148cm
-1)
1HNMR (proton nmr spectra):
Proton 1: δ=6.76 * 10
-6, s=1.0
Proton 2: δ=7.10 * 1
-6, s=2.03
Proton 3: δ=7.80 * 10
-6, s=1.99
Proton 4: δ=7.34 * 10
-6, s=0.99
Proton 5: δ=7.62 * 10
-6, s=1.0
Proton 6: δ=7.87 * 10
-6, s=0.98
Proton 7: δ=8.04 * 10
-6, s=0.98
Proton 8: δ=7.36 * 10
-6, s=1.00
Proton 9: δ=7.47 * 10
-6, s=2.05
Proton 10: δ=7.41 * 10
-6, s=2.02
Proton 11: δ=5.19 * 10
-6, s=2.0
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:
K98.9I(82.4)N(42.3)K
The transformation behavior that meets thermotropic liquid crystal.
By orthogonal polarizing microscope institute's synthetic sample is observed: sample presents needle-like crystal under the normal temperature, and 149 ℃ of left and right sides sample fusions, the visual field presents the even black of a slice, illustrates after crystal melts directly to become isotropic liquid.Be heated to 160 ℃ it is fully fused, lower the temperature with the speed of 5 ℃/min again.To about 130 ℃, occur colored drop in the black background, and it is moving to continue to flow, and occurs the cross frosting phenomenon in the part drop, demonstrates typical spherolite texture, shows that sample exists with the nematic liquid crystal attitude at present.This mesomorphic phase is 30 ℃ of left and right sides crystallizations.This phase behavior shows that to benzyloxy styracin-2-fluoro-4-4-hydroxy-benzonitrile ester be monotropic thermotropic liquid crystal.
More than explanation is suitable as liquid crystal composite ideal moiety used in the liquid-crystal display to benzyloxy styracin-2-fluoro-4-4-hydroxy-benzonitrile ester about the test result of liquid crystal property, can be used as the liquid crystal monomer that is mixed in the liquid-crystal display and uses.Can be applicable in the used liquid crystal composite material of liquid-crystal displays such as TN, STN, TFT.
Claims (2)
1. a liquid crystalline cpd---to benzyloxy styracin-2-fluoro-4-4-hydroxy-benzonitrile ester, its structural formula is
2. a liquid crystalline cpd---the preparation method to benzyloxy styracin-2-fluoro-4-4-hydroxy-benzonitrile ester is characterized in that
1) under the potential of hydrogen of pH＞10,50～80 ℃ temperature, in solution, add halogenation benzyl and p-Coumaric Acid, make both that condensation reaction take place, generate the benzyloxy styracin,
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, impels benzyloxy styracin and the paired benzyloxy styracin of 2-fluoro-4-4-hydroxy-benzonitrile dehydrating condensation-2-fluoro-4-4-hydroxy-benzonitrile ester.
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| CNB2005100437118A CN1315795C (en) | 2005-06-08 | 2005-06-08 | Novel LCD compound p-phenyl-methoxy cinnamic acid -2-fluoro-4-hydroxy- benzonitrile ester and its preparation method |
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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 |
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| (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 荣国斌等，液晶与显示，第12卷第3期 1997 * |
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