CN101280196B - Four-ring liquid crystal compounds - Google Patents
Four-ring liquid crystal compounds Download PDFInfo
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- CN101280196B CN101280196B CN2008101105490A CN200810110549A CN101280196B CN 101280196 B CN101280196 B CN 101280196B CN 2008101105490 A CN2008101105490 A CN 2008101105490A CN 200810110549 A CN200810110549 A CN 200810110549A CN 101280196 B CN101280196 B CN 101280196B
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Abstract
The invention discloses four-ring liquid crystal compound; the structure general formula is indicated in (1); wherein, the R is straight-chain alkane or straight-chain alkoxy with the carbon number of 1-10. The four-ring liquid crystal compound has the advantages of high clearing point, good miscibility and being applicable to the liquid crystal display.
Description
Technical field
The present invention relates to a kind of four-ring liquid crystal compounds, be used for the liquid crystal display material field.
Background technology
Along with the developing rapidly of lcd technology, higher requirement is proposed also liquid crystal display material in recent years.The liquid crystal material that is used for flat pannel display is normally mixed by a certain percentage by the liquid crystalline cpd of 5～20 kinds of different qualities, each compound is to the contribution difference of dispensing liquid crystal, the liquid crystalline cpd component that for example existing polarity is bigger also has nonpolar liquid crystalline cpd component; The higher liquid crystal components of clearing point is arranged, the liquid crystal components that clearing point is low, viscosity is little is also arranged, mix the formation prescription and can learn from other's strong points to offset one's weaknesses later, obtain optimal display performance.
Structural formula liquid crystalline cpd as follows is disclosed in U.S. Pat 4419264A1:
R wherein
1, R
2Be alkyl or the alkoxyl group that is no more than 8 carbon atoms, one of them or two substituent X are fluorine, and all the other substituent X are hydrogen.This four-ring liquid crystal compounds has very high clearing point, but viscosity is also bigger, and intermiscibility is relatively poor.
Summary of the invention
Technical problem to be solved by this invention is to overcome deficiency of the prior art, and a kind of not only clearing point height is provided, and the four-ring liquid crystal compounds that viscosity is little, intermiscibility is good, the low temperature display performance is good.
Compound involved in the present invention is the less four-ring liquid crystal compounds of a kind of polarity, molecule is bar-shaped linear structure, contain four six annulus, the clearing point height, and insert the ethylene bridged bond that can rotate freely at minute subcenter, thereby intermiscibility is good, and the low temperature display performance improves, and is suitable as a kind of high clearing point component and uses at the mixed liquid crystal prescription.
The present invention is a kind of four-ring liquid crystal compounds, is characterized in that general structure is shown in (1):
Wherein R is that carbon number is 1～10 straight chained alkyl or straight chain alkoxyl group.
Second characteristics of the present invention are that the preferred carbon number of R is 1～7 straight chained alkyl or straight chain alkoxyl group.
The 3rd characteristics of the present invention are that the preferred carbon number of R is 1～5 straight chained alkyl or straight chain alkoxyl group.
The 4th characteristics of the present invention are that structural formula is as follows:
The 5th characteristics of the present invention are that structural formula is as follows:
To be not limited to carbon number be 1～10 straight chained alkyl or straight chain alkoxyl group to R among the present invention, and R also can be that carbon number is 1～10 the alkyl that has side chain, alkoxyl group, and R can also fluorine or chlorine.
The compounds of this invention has following advantage:
1) the present invention compares with the known structure tetracyclic compound, and it introduces the ethylene bridged bond, and its molecular conjugation degree reduces, and not only intermiscibility improves, and has the little characteristics of viscosity, and the low temperature display performance is good.
2) the present invention not only intermiscibility improve, and kept the high advantage of four-ring liquid crystal compounds clearing point.
Synthetic route of the present invention is as follows:
The preparation method of The compounds of this invention comprises following steps:
(1) 4-methoxybenzaldehyde and sodium borohydride carry out reduction reaction and obtain 4-anisole methyl alcohol;
(2) 4-anisole methyl alcohol and concentrated hydrochloric acid carry out chlorination and obtain 4-methoxybenzyl chlorine;
(3) 4-methoxybenzyl chlorine and magnesium powder prepared in reaction Grignard reagent carry out linked reaction again and make 1, two (4-p-methoxy-phenyl) ethane of 2-;
Two (4-p-methoxy-phenyl) ethane of (4) 1,2-react with Hydrogen bromide, acetate as solvent carry out demethylating reaction obtain 4,4 '-(ethylene) biphenol;
(5) 4,4 '-(ethylene) biphenol obtains 4,4 in catalytic hydrogenation '-(ethylene) two hexalin;
(6) 4,4 '-(ethylene) two hexalin obtain 4,4 under oxidation '-(ethylene) two pimelinketone;
(7) 4-alkyl bromobenzene or 4-alkoxyl group bromobenzene Grignard reagent and 4,4 '-(ethylene) two pimelinketone couplings, obtain tertiary alcohol derivative after the hydrolysis;
(8) tertiary alcohol derivative is dehydrated into ene derivative under the catalysis of sulfuric acid hydrogen clock;
(9) ene derivative carries out catalytic hydrogenation, and recrystallization obtains target compound of the present invention.
Embodiment
Below in conjunction with embodiment content of the present invention is described further.
Embodiment 11, the preparation of two (4-(4-ethylphenyl) cyclohexyl) ethane of 2-
The preparation of step 1:4-anisole methyl alcohol
11.4g sodium borohydride, 200ml ethanol are joined in the 500ml there-necked flask, stir down slowly dropping 134g 4-methoxybenzaldehyde, the control rate of addition makes temperature of reaction be no more than 35 ℃, drips off the back and stirs continuation reaction down 1 hour.Pouring reactant into the 200ml mass concentration is in 5% the dilute hydrochloric acid, with 200ml toluene extracting twice.Remove toluene under reduced pressure and get oily liquids 128g, the yield 94% of 4-anisole methyl alcohol.
The preparation of step 2:4-methoxybenzyl chlorine
To go up step reaction gained 4-anisole methyl alcohol 128g and join in the 500ml there-necked flask, and add concentrated hydrochloric acid 300ml, stirring reaction is 2 hours under the room temperature.Divide oil-yielding stratum, water layer 200ml petroleum ether extraction.Sherwood oil and oil reservoir merge, and are washed to neutrality with 5% sodium bicarbonate, the Anhydrous potassium carbonate drying.Remove sherwood oil under reduced pressure, distillation gets colourless oil liquid 109g, the yield 84% of 4-methoxybenzyl chlorine.
Step 3:1, two (4-p-methoxy-phenyl) ethane of 2-
With magnesium powder 3g, a granule iodine in the 20mL tetrahydrofuran (THF) adding 250mL four-hole bottle, is warmed up to 60 ℃, begins to drip 31g4-methoxybenzyl chlorine and 80mL tetrahydrofuran (THF) mixing solutions under the nitrogen protection.Dripped off in about 0.5～1 hour, reheat is warming up to backflow, reacts 5 hours.Naturally cool to room temperature, pour in the dilute hydrochloric acid, leach solid, this solid gets white solid 16g with ethanol and ethyl acetate mixture recrystallization, and 1, two (4-p-methoxy-phenyl) ethane recoveries 66% of 2-.
Step 4:4,4 '-(ethylene) biphenol
With 12.1g 1, two (4-p-methoxy-phenyl) ethane of 2-, the 100mL Glacial acetic acid, the Hydrogen bromide of 50mL40% joins in the 250mL reaction flask, heats to backflow, reacts 9 hours.Cool overnight is separated out crystal.Filter, washing is dried, and obtains the grey crystal 4,4 '-(ethylene) biphenol 10g, 4,4 '-(ethylene) biphenol yield 93.5%.
Step 5:4,4 '-(ethylene) two hexalin
With 18g4,4 '-(ethylene) biphenol, 1g yellow soda ash, 2g5% palladium/carbon, 200mL ethanol adds in the autoclave.Feeding the hydrogen first pressing is 4MPa, is warming up to 120 ℃ of reactions 6 hours.Cooling, elimination catalyzer, concentrating under reduced pressure get white solid 18g.
Step 6:4,4 '-(ethylene) two pimelinketone
18g chromium trioxide, the 26.5g vitriol oil, 30g water are made into chromic acid aqueous solution, standby.In the 500mL there-necked flask, add 4,4 '-(ethylene) two hexalin 23g, acetone 300mL, stirring and dissolving.Ice-water bath cools to below 10 ℃, drips the chromic acid aqueous solution for preparing, and the control rate of addition makes temperature of reaction be no more than 15 ℃, dropwises in about 0.5 hour.Drip off back insulation reaction 1.5 hours, add Virahol 5mL, filter.The filter cake washing with acetone, filtrate decompression concentrates.Add the 30mL sherwood oil, separate out crystal.Filter crystal 18.5g, gas-chromatography content is 98%, 4,4 '-yield 85.6% of (ethylene) two pimelinketone.
Structure is identified:
IR(KBr，cm
-1)：2951，2922，2900，2853，1712(vc＝o)，1162，938。
1HNMR(500MHz，CDCl
3，δ)：1.256～1.445(8H，m)；1.700(2H，s)；2.055(4H，d)；2.296～2.399(8H，m)。
Above structure appraising datum show the gained compound be really intermediate 4,4 '-(ethylene) two pimelinketone.
Step 7:4,4 '-(ethylene) two ((4-ethylphenyl) hexalin)
Under the nitrogen protection 2.9g magnesium powder, 30mL exsiccant tetrahydrofuran (THF), a granule iodine are joined in the 250mL four-hole bottle.Dropping is dissolved with the dry tetrahydrofuran solution of 18.5g4-bromine ethylbenzene 70mL.The control rate of addition remains between 45 ℃～55 ℃ temperature of reaction, drips off in about 1 hour, and insulation reaction is 0.5 hour again.Dropping is dissolved with 10.1g4,4 '-the dry tetrahydrofuran solution of the 50mL of (ethylene) two pimelinketone, drip off post-heating backflow 2h.Be cooled to room temperature, pour reactant in ice and dilute hydrochloric acid solution hydrolysis.Add 100mL toluene extraction 2 times, be washed to neutrality.Merge organic phase, anhydrous magnesium sulfate drying.
Step 8:1, two (4-(4-the ethylphenyl)-1-cyclohexenyl) ethane of 2-
Previous step is reacted gained solution join in the reaction flask, add tosic acid 1.0g, be heated to backflow, divide water.React after 2 hours, TLC detects dehydration fully.Be cooled to room temperature, with the washing of 5% aqueous sodium carbonate, be washed to neutrality again, anhydrous magnesium sulfate drying earlier.Remove toluene under reduced pressure, the sherwood oil recrystallization gets white crystal 12.5g.
Step 9:1, two (4-(4-ethylphenyl) cyclohexyl) ethane of 2-
With 10.0g 1, two (4-(4-the ethylphenyl)-1-cyclohexenyl) ethane of 2-, 1.0g 5% palladium/carbon, the 50mL tetrahydrofuran (THF) adds in the reaction flask, carries out catalytic hydrogenation under the normal temperature and pressure 8 hours.Filtration catalizer removes solvent under reduced pressure, gets white crystal 4.0g with the sherwood oil recrystallization, gas chromatographic purity 99.5%.
Structure is identified:
Ultimate analysis: C
30H
42
Theoretical value: C:89.49, H:10.51
Measured value: C:89.28, H:10.43.
MS(EI，70ev)：402(10，M
+)，145(47)，132(58)，119(100)，117(99)，105(22)，91(58)，81(13)，67(13)，55(17)。
IR(KBr，cm
-1)：3048，3014，2913，2843，1897，1633，1513，1447，823，554。
1HNMR(500MHz，CDCl
3，δ)：1.018～1.085(m，4H)，1.228(t，6h，J＝7.5Hz，CH
3)，1.263(s，6H)，1.403～1.486(m，4H)，1.861～1.902(m，8H)，2.409～2.471(m，2H)，2.620(q，4H，J＝7.5Hz，CH
2)，7.128(s，8H，Ar-H)。
Above structure appraising datum shows that institute's synthetic compound is 1 really, two (4-(4-ethylphenyl) cyclohexyl) ethane of 2-.
Utilize DSC that the transformation temperature of liquid crystal is tested, fusing point is 102.2 ℃ to the smectic phase transition temperature, and smectic phase is 172.9 ℃ to the nematic Phase temperature, and clearing point is 219.6 ℃, the liquid crystal phase region is 117.4 ℃, and the result shows that the compound clearing point height and the liquid crystal phase region that are synthesized are wide.
Embodiment 2～embodiment 5
Embodiment 2, embodiment 3, embodiment 4, embodiment 5 are respectively with the 4-bromine ethylbenzene in 4-toluene bromide, 4-bromine n-propylbenzene, 4-bromine n-pentyl penta benzene, 4-bromine n-heptylphenyl difference alternate embodiment 1 step 7, adopt preparation method substantially the same manner as Example 1 to obtain: 1, two (4-(4-aminomethyl phenyl) cyclohexyl) ethane of 2-; 1, two (4-(the 4-n-propyl phenyl) cyclohexyl) ethane of 2-; 1, two (4-(the 4-n-pentyl phenyl) cyclohexyl) ethane of 2-; 1, two (4-(the 4-n-heptyl phenyl) cyclohexyl) ethane of 2-.
Embodiment 6～embodiment 9
4-bromine ethylbenzene in embodiment 6, embodiment 7, embodiment 8, embodiment 9 usefulness 4-bromine methoxy benzene, 4-bromine positive propoxy benzene, 4-bromine n-pentyloxy penta benzene, 4-bromine oxygen base in positive heptan benzene difference alternate embodiment 1 step 7, adopt the preparation method identical to obtain with embodiment 1: 1,2-pair of (4-(4-p-methoxy-phenyl) cyclohexyl) ethane; 1, two (4-(the 4-positive propoxy phenyl) cyclohexyl) ethane of 2-; 1, two (4-(the 4-n-pentyloxy phenyl) cyclohexyl) ethane of 2-; 1, two (4-(4-oxygen base in the positive heptan phenyl) cyclohexyl) ethane of 2-.
Claims (5)
1. four-ring liquid crystal compounds, its general structure is shown in (1):
Wherein R is that carbon number is 1～10 straight chained alkyl or straight chain alkoxyl group.
2. according to the described four-ring liquid crystal compounds of claim 1, wherein R is that carbon number is 1～7 straight chained alkyl or straight chain alkoxyl group.
3. according to the described four-ring liquid crystal compounds of claim 2, wherein R is that carbon number is 1～5 straight chained alkyl or straight chain alkoxyl group.
4. according to the described four-ring liquid crystal compounds of claim 3, it is characterized in that structural formula is as follows:
5. according to the described four-ring liquid crystal compounds of claim 3, it is characterized in that structural formula is as follows:
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| CA2745119A1 (en) * | 2008-12-03 | 2010-06-10 | Presidio Pharmaceuticals, Inc. | Inhibitors of hcv ns5a |
| CN109265330A (en) * | 2018-10-25 | 2019-01-25 | 广州中大南沙科技创新产业园有限公司 | A kind of preparation method of 4-(4-hydroxyphenyl)-2-butanone |
| CN114621044A (en) * | 2020-12-12 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing bibenzyl compound |
Citations (3)
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|---|---|---|---|---|
| CN1158601A (en) * | 1994-09-22 | 1997-09-03 | 智索公司 | Chlorobenzene derivative and liquid-crystal compsn. containing the same |
| US6074708A (en) * | 1997-12-22 | 2000-06-13 | Sharp Kabushiki Kaisha | Photoinitiator photopolymerizable resin composition, polymer and liquid crystal display device |
| WO2005085208A1 (en) * | 2004-03-09 | 2005-09-15 | Nissan Chemical Industries, Ltd. | 2,4,5-triaryl substituted imidazole compound and 1,2,4,5-tetraaryl substituted imidazole compound |
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2008
- 2008-06-03 CN CN2008101105490A patent/CN101280196B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1158601A (en) * | 1994-09-22 | 1997-09-03 | 智索公司 | Chlorobenzene derivative and liquid-crystal compsn. containing the same |
| US6074708A (en) * | 1997-12-22 | 2000-06-13 | Sharp Kabushiki Kaisha | Photoinitiator photopolymerizable resin composition, polymer and liquid crystal display device |
| WO2005085208A1 (en) * | 2004-03-09 | 2005-09-15 | Nissan Chemical Industries, Ltd. | 2,4,5-triaryl substituted imidazole compound and 1,2,4,5-tetraaryl substituted imidazole compound |
Non-Patent Citations (10)
| Title |
|---|
| Bates,Robert B |
| Bates,Robert B;et al.Preperations and reactions of symmetrical dimethylenebiphenyl dianions.《Journal of Organic Chemistry》.1989,311-317. * |
| Brand,K |
| Brand,K;et al.Thiophenois.XII.Triphenylmethane serires.《Journal fuer Praktische Chemie》.1928,199-213. * |
| Dabrowski,Roman S |
| Dabrowski,Roman S;eet al.Low-viscosity mixtures for STN and TN displays.《Liquid Crystals》.2000,41-48. * |
| eet al.Low-viscosity mixtures for STN and TN displays.《Liquid Crystals》.2000,41-48. |
| et al.Preperations and reactions of symmetrical dimethylenebiphenyl dianions.《Journal of Organic Chemistry》.1989,311-317. |
| et al.Thiophenois.XII.Triphenylmethane serires.《Journal fuer Praktische Chemie》.1928,199-213. |
| 张浥静.2008101105490.《STN检索记录》.2010, * |
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