CN101113336A - Dimer liquid crystals compound with halogens on side - Google Patents
Dimer liquid crystals compound with halogens on side Download PDFInfo
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- CN101113336A CN101113336A CNA2006101079459A CN200610107945A CN101113336A CN 101113336 A CN101113336 A CN 101113336A CN A2006101079459 A CNA2006101079459 A CN A2006101079459A CN 200610107945 A CN200610107945 A CN 200610107945A CN 101113336 A CN101113336 A CN 101113336A
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- trans
- cyclohexyl
- phenoxy group
- cholesteryl ester
- chloro
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Abstract
The invention discloses a dimer liquid crystals compound expressed by a general formula (1) and contains cholesteryl and trans-cyclohexyl phenyl with benzene ring with halogen at the side of the benzene ring . The invention aims at providing a polarization agent of liquid crystal mixtures or dimer liquid crystals compound of cholesteric phase with a low and wide temperature range, low rotation viscosity and high polarization force and a preparing method thereof. R in the compound of the general formula (1) provided in the invention is a gaseous normal alkyl with 5-7 carbon atoms, with n being equal to 3-5, 7 and X being equal to F or CI. The compound in the invention has low and wide temperature range of liquid crystalline phase and presents a single cholesteric phase with practical application value, stable physical and chemical properties, comparatively lower viscosity and comparatively higher polarization force. The compound which is applicable to components of a liquid crystals display, a temperature sensor and so on and is capable of being used as the polarization agent of components of liquid crystals materials and liquid crystals mixtures has wide application prospects.
Description
Technical field:
The present invention relates to a kind of liquid crystal compound in mesomorphic structure that contains halogen-containing trans cyclohexyl phenyl in side and cholesteryl and contain the liquid crystal media of at least a general formula (I) compound and the electro-optical display that comprises this liquid crystal media.
Background technology:
Cholesterol is the chipal compounds in the abundant cheapness that exists of nature, so be that chiral source can be synthesized multiple chiral nematic phase (cholesteryl phase) liquid crystalline cpd (A.I.Galatina et al, Mol.cryst.liq.cryst., 140,11-81,1986) with it.Therefore cholesteric liquid crystal is with a wide range of applications because its spirane structure has characteristics such as opticity, the diffusing look of selective light, rotatory polarization dichroism.But owing to great majority with the cholesterol be rigid nuclear liquid crystalline cpd transformation temperature height, liquid crystal range is narrow and reason such as viscosity height, its application is very limited.On the other hand, because various new smectic liquid crystal (S of the later stage seventies and the initial stage eighties
A-I), discotic mesogenic, blue phase liquid crystal and lytropic liquid crystals find in succession make scientist's research interest redirect to pure liquid crystal science, making cholesteryl is that the liquid crystal of rigid nuclear has become " Cinderella " (the GS.Chilaya and L.N.Lisetski in the liquid crystal family for the moment, Mol.cryst.liq.cryst., 140,243-286,1986).Up to delivering two mesomorphic compounds that contain cholesteryl because the chirality influence of cholesteryl is quite interesting thermal behavior (F.Hardouin, M.F.Achard, Jung-I1.Jin andYong-kuk Yun, J.Phys.II France 5,927-935,1995. as compound K 15 C → S
Ainc→ S
C*→ S
Ainc→ S
C*→ TGB → N
*→ BP → I) and can regulate (C.V.Yelamaggad, Mol.Cryst.liq.cryst., 326,149-153,19993.) after the achievement in research of transformation temperature by spacer and terminal chain, this class liquid crystal has caused the extensive concern of scientific circles again.
Introducing fluorine atom can improve the viscosity of liquid crystal and reduce liquid crystal temperature and clearing point (G.W.Gray, Mol.Cryst Liq.Cryst., 204,43-64,1991 in the side of liquid crystal molecule rigid nuclear; M.A.Osman, Mol.Cryst Liq.Cryst., 1284,45-63,1985; Chu Chuan Dong, Peter Styring, John W.Goodby etc, J.Mater.Chem., 1999,9,1669-1677).
Summary of the invention:
The purpose of this invention is to provide the liquid crystal compound in mesomorphic structure that contains halogen-containing trans cyclohexyl phenyl in side and cholesteryl.Corresponding unsubstituted two mesomorphic compounds of this compounds contrast also have low transformation temperature, have good physics and chemical stability simultaneously.This compounds presents the liquid crystal state of single and low and wide cholesteryl phase.
Provided by the present invention is the compound of general formula (I):
R is the alkyl of 3-9 carbon atom in the formula, n=3-5,7, X=F, Cl.
Specifically, the compound of general formula (I) is a kind of of following member:
4-(4-trans-(4-amyl group cyclohexyl)-2-chloro-phenoxy group) butyric acid cholesteryl ester (I
01)
5-(4-trans-(4-amyl group cyclohexyl)-2-chloro-phenoxy group) valeric acid cholesteryl ester (I
02)
6-(4-trans-(4-amyl group cyclohexyl)-2-chloro-phenoxy group) caproic acid cholesteryl ester (I
03)
Sad cholesteryl ester (the I of 8-(4-trans-(4-amyl group cyclohexyl)-2-chloro-phenoxy group)
04)
4-(4-trans-(4-hexyl cyclohexyl)-2-chloro-phenoxy group) butyric acid cholesteryl ester (I
05)
5-(4-trans-(4-hexyl cyclohexyl)-2-chloro-phenoxy group) valeric acid cholesteryl ester (I
06)
6-(4-trans-(4-hexyl cyclohexyl)-2-chloro-phenoxy group) caproic acid cholesteryl ester (I
07)
Sad cholesteryl ester (the I of 8-(4-trans-(4-hexyl cyclohexyl)-2-chloro-phenoxy group)
08)
4-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group) butyric acid cholesteryl ester (I
09)
5-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group) valeric acid cholesteryl ester (I
10)
6-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group) caproic acid cholesteryl ester (I
11)
Sad cholesteryl ester (the I of 8-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group)
12)
4-(4-trans-(4-amyl group cyclohexyl)-2-fluoro-phenoxy group) butyric acid cholesteryl ester (I
13)
5-(4-trans-(4-amyl group cyclohexyl)-2-fluoro-phenoxy group) valeric acid cholesteryl ester (I
14)
6-(4-trans-(4-amyl group cyclohexyl)-2-fluoro-phenoxy group) caproic acid cholesteryl ester (I
15)
Sad cholesteryl ester (the I of 8-(4-trans-(4-amyl group cyclohexyl)-2-fluoro-phenoxy group)
16)
4-(4-trans-(4-hexyl cyclohexyl)-2-fluoro-phenoxy group) butyric acid cholesteryl ester (I
17)
5-(4-trans-(4-hexyl cyclohexyl)-2-fluoro-phenoxy group) valeric acid cholesteryl ester (I
18)
6-(4-trans-(4-hexyl cyclohexyl)-2-fluoro-phenoxy group) caproic acid cholesteryl ester (I
19)
Sad cholesteryl ester (the I of 8-(4-trans-(4-hexyl cyclohexyl)-2-fluoro-phenoxy group)
20)
4-(4-trans-(4-heptyl cyclohexyl)-2-fluoro-phenoxy group) butyric acid cholesteryl ester (I
21)
5-(4-trans-(4-heptyl cyclohexyl)-2-fluoro-phenoxy group) valeric acid cholesteryl ester (I
22)
6-(4-trans-(4-heptyl cyclohexyl)-2-fluoro-phenoxy group) caproic acid cholesteryl ester (I
23)
Sad cholesteryl ester (the I of 8-(4-trans-(4-heptyl cyclohexyl)-2-fluoro-phenoxy group)
24)
Second purpose of the present invention provides the method for preparing general formula (I) compound.Be to realize this purpose, the present invention by the following technical solutions: the cholesterol fatty acid ester of trans (4-alkyl-cyclohexyl)-2-halogenated phenol of 4-and terminal bromo is carried out substitution reaction obtain general formula (I) compound, wherein R is the alkyl of 3-9 carbon atom, n=3-5,7, X=F, Cl.
In addition, also comprise the preparation of the needed part intermediate of synthesising target compound.
1.1-trans (4-amyl group cyclohexyl)-3-chlorobenzene
2.1-trans (4-heptyl cyclohexyl)-3-chlorobenzene
3.4-trans (4-heptyl cyclohexyl)-2-chloroacetophenone
4.4-trans (4-heptyl cyclohexyl)-2-chlorophenol
The present invention will be further described below in conjunction with specific embodiment.
Embodiment
Embodiment, the sad cholesteryl ester of preparation 8-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group), concrete steps are as follows:
1, trans (4-heptyl the cyclohexyl)-3-chlorobenzene of preparation 1-
In freshly prepd 0.1 mole of 3-chloro-phenyl-magnesium bromide Grignard reagent, under cooling and stirring, be added dropwise to the diethyl ether solution of equimolar 4-n-heptyl pimelinketone, finish and refluxed 1 hour.Pour in the concentrated hydrochloric acid that contains trash ice, tell the ether layer, water layer ether extraction 2 times merge, and aqueous sodium carbonate washs once, and anhydrous sodium sulfate drying desolventizes, and resistates is dissolved in toluene, and the water trap reflux dewatering is installed under Catalyzed by p-Toluenesulfonic Acid.Distill out toluene, add sherwood oil, concussion, filter out undissolved tosic acid, concentrate, silica gel column chromatography obtains 1-(4-heptyl-1-cyclohexenyl)-3-chlorobenzene, further use palladium carbon to do the suitable back mixing compound that catalyst hydrogenation gets (4-heptyl cyclohexyl)-3-chlorobenzene, use potassium tert.-butoxide about 110 degree, to use DMF to do trans (4-heptyl the cyclohexyl)-3-chlorobenzene of 1-that solvent reaction obtained transconfiguration in 1 hour, colourless liquid
1HNMR 6:7.08-7.25 (m, 4H), 2.46 (t, J=12.1Hz, 1H), 1.88 (m, 4H), 0.92-1.64 (m, 17H), 0.89 (t, 3H).
2, trans (4-heptyl the cyclohexyl)-2-chloroacetophenone of preparation 4-
Add 0.11 mole of anhydrous AlCl in exsiccant 600ml methylene dichloride kind
3, be cooled to 5-10 ℃ and drip 0.1 mole of Acetyl Chloride 98Min..Be cooled to trans (4-heptyl the cyclohexyl)-3-chlorobenzene of adding 1-below 0 ℃ then, finish at 0 ℃ and continue to stir 3 hours.In mixture impouring ice, tell organic layer, the water layer dichloromethane extraction merges organic layer, uses 5%HCl successively, water washing.Anhydrous MgSO
4Dry.Filter distilling off solvent, recrystallizing methanol.Get 61-63 ℃ of white plates solid mp.Can get trans (4-the alkyl-cyclohexyl)-2-halo acetophenone of other 4-with method.
3, trans (4-heptyl the cyclohexyl)-2-chlorophenol of preparation 4-.
0.05 after the chloroformic solution of mole trans (4-heptyl the cyclohexyl)-2-chloro-acetophenone of 4-and freshly prepd 100 milliliters of peroxybenzoic acid at room temperature stirred 48 hours, mixture was used NaHSO successively
3Solution, NaHCO
3Solution, H
2O washs.Distill out chloroform and obtain slightly yellowy oily matter.Add 25 milliliters of ethanol, 1 ml water, 0.2 gram NaOH refluxed 4 hours.Regulate PH＜7, ethyl acetate extraction, anhydrous Na SO with hydrochloric acid
4Dry.Desolventize and use silica gel column chromatography, eluent CHCl
3, get the white plates solid.mp?65.8℃，
1HNMR?δ：7.16(s，1H)，7.03(d，2H)，6.94(d，2H)，5.44(s，1H)，2.39(t，J＝12.0Hz，1H)，1.88(m，4H)，0.93-1.61(m，17H)，0.89(t，3H).
Can get trans (4-the alkyl-cyclohexyl)-2-halogenated phenol of other 4-with method.
4, preparation 8-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group) trans (4-heptyl the cyclohexyl)-2-chlorophenol of sad cholesteryl ester 4-refluxed in butanone solvent 4 hours with the cholesterol fatty acid ester that waits mole terminal bromo, steaming desolventizes, dissolve with methylene dichloride, filter out solid impurity, concentrate, silicagel column separates, and methylene dichloride is as eluent, acetone recrystallization gets white crystal.Yield 65%.
1HNMR?δ：7.22(s，1H)，7.04(d，J＝8.1Hz，1H)，6.85(d，J＝8.1Hz，1H)，5.39(m，1H)，4.65(m，1H)，4.06(t，J＝5.4Hz，2H)，2.54(t，2H)，0.70-2.34(m，78H).DSC Cr?78.1 N
* 121.6 I。
Use the same method and to make other compounds of general formula (I)
Compound of the present invention has the lower transformation temperature and the phase transformation range of broad, has good physics and chemical stability simultaneously.This compounds presents the liquid crystal state of single and low and wide cholesteryl phase, have simultaneously high play inclined to one side power and viscosity lower, be 1.3 as the viscosity of 5F5
Pas. this compounds has broad application prospects at aspects such as liquid-crystal display and temperature sensing.
Claims (6)
1. the compound of general formula (I):
Wherein R is the straight chained alkyl of 5-7 carbon atom, n=3～5 or 7, and X is F or C1.
2. the liquid crystal media and the electro-optical display that comprises this liquid crystal media that contain at least a general formula (I) compound.
3. compound according to claim 1 is characterized in that: this compound is a kind of of following member:
4-(4-trans-(4-amyl group cyclohexyl)-2-chloro-phenoxy group) butyric acid cholesteryl ester (I
01)
5-(4-trans-(4-amyl group cyclohexyl)-2-chloro-phenoxy group) valeric acid cholesteryl ester (I
02)
6-(4-trans-(4-amyl group cyclohexyl)-2-chloro-phenoxy group) caproic acid cholesteryl ester (I
03)
Sad cholesteryl ester (the I of 8-(4-trans-(4-amyl group cyclohexyl)-2-chloro-phenoxy group)
04)
4-(4-trans-(4-hexyl cyclohexyl)-2-chloro-phenoxy group) butyric acid cholesteryl ester (I
05)
5-(4-trans-(4-hexyl cyclohexyl)-2-chloro-phenoxy group) valeric acid cholesteryl ester (I
06)
6-(4-trans-(4-hexyl cyclohexyl)-2-chloro-phenoxy group) caproic acid cholesteryl ester (I
07)
Sad cholesteryl ester (the I of 8-(4-trans-(4-hexyl cyclohexyl)-2-chloro-phenoxy group)
08)
4-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group) butyric acid cholesteryl ester (I
09)
5-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group) valeric acid cholesteryl ester (I
10)
6-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group) caproic acid cholesteryl ester (I
11)
Sad cholesteryl ester (the I of 8-(4-trans-(4-heptyl cyclohexyl)-2-chloro-phenoxy group)
12)
4-(4-trans-(4-amyl group cyclohexyl)-2-fluoro-phenoxy group) butyric acid cholesteryl ester (I
13)
5-(4-trans-(4-amyl group cyclohexyl)-2-fluoro-phenoxy group) valeric acid cholesteryl ester (I
14)
6-(4-trans-(4-amyl group cyclohexyl)-2-fluoro-phenoxy group) caproic acid cholesteryl ester (I
15)
Sad cholesteryl ester (the I of 8-(4-trans-(4-amyl group cyclohexyl)-2-fluoro-phenoxy group)
16)
4-(4-trans-(4-hexyl cyclohexyl)-2-fluoro-phenoxy group) butyric acid cholesteryl ester (I
17)
5-(4-trans-(4-hexyl cyclohexyl)-2-fluoro-phenoxy group) valeric acid cholesteryl ester (I
18)
6-(4-trans-(4-hexyl cyclohexyl)-2-fluoro-phenoxy group) caproic acid cholesteryl ester (I
19)
Sad cholesteryl ester (the I of 8-(4-trans-(4-hexyl cyclohexyl)-2-fluoro-phenoxy group)
20)
4-(4-trans-(4-heptyl cyclohexyl)-2-fluoro-phenoxy group) butyric acid cholesteryl ester (I
21)
5-(4-trans-(4-heptyl cyclohexyl)-2-fluoro-phenoxy group) valeric acid cholesteryl ester (I
22)
6-(4-trans-(4-heptyl cyclohexyl)-2-fluoro-phenoxy group) caproic acid cholesteryl ester (I
23)
Sad cholesteryl ester (the I of 8-(4-trans-(4-heptyl cyclohexyl)-2-fluoro-phenoxy group)
24)
4. method for preparing the described compound of claim 1 is carried out condensation reaction with 4-(trans-the 4-alkyl-cyclohexyl)-2-halogenated phenol and ω-bromo fatty acid cholesterol ester and is obtained.Wherein said alkyl is the straight chained alkyl of 5-7 carbon, and halogen is a fluorine or chlorine, and lipid acid is 4-6, the lipid acid of 8 carbon.Its response feature is with the 2-butanone of higher as reaction solvent yield height when using acetone.
5. the described method of claim 4 is characterized in that the preparation of described 4-(trans-the 4-alkyl-cyclohexyl)-2-chlorophenol may further comprise the steps:
1) be feedstock production 3-(trans-the 4-alkyl-cyclohexyl) chlorobenzene with 4-alkyl cyclohexanone and 3-chloro-phenyl-magnesium bromide;
2) 3-(trans-the 4-alkyl-cyclohexyl) chlorobenzene is feedstock production 4-(trans-the 4-alkyl-cyclohexyl)-2-chlorophenol.
6. the described method of claim 4, the preparation that it is characterized in that described 4-(trans-the 4-alkyl-cyclohexyl)-2-fluorophenol are to be feedstock production 4-(trans-the 4-alkyl-cyclohexyl)-2-fluorophenol by 3-(trans-the 4-alkyl-cyclohexyl) fluorobenzene.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101079459A CN101113336A (en) | 2006-07-25 | 2006-07-25 | Dimer liquid crystals compound with halogens on side |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2006101079459A CN101113336A (en) | 2006-07-25 | 2006-07-25 | Dimer liquid crystals compound with halogens on side |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159996A (en) * | 2012-03-07 | 2014-11-19 | 富士胶片株式会社 | Compound, liquid crystal composition, polymer material and film |
| CN104822800A (en) * | 2012-12-10 | 2015-08-05 | 默克专利股份有限公司 | BImesogenic compounds and mesogenic media |
-
2006
- 2006-07-25 CN CNA2006101079459A patent/CN101113336A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104159996A (en) * | 2012-03-07 | 2014-11-19 | 富士胶片株式会社 | Compound, liquid crystal composition, polymer material and film |
| CN104159996B (en) * | 2012-03-07 | 2016-01-20 | 富士胶片株式会社 | Compound, liquid-crystal composition, macromolecular material and film |
| CN104822800A (en) * | 2012-12-10 | 2015-08-05 | 默克专利股份有限公司 | BImesogenic compounds and mesogenic media |
| TWI611005B (en) * | 2012-12-10 | 2018-01-11 | 馬克專利公司 | Bimesogenic compounds and mesogenic media |
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