CN102757793A - Liquid crystal compound and application thereof - Google Patents
Liquid crystal compound and application thereof Download PDFInfo
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- CN102757793A CN102757793A CN2012102654881A CN201210265488A CN102757793A CN 102757793 A CN102757793 A CN 102757793A CN 2012102654881 A CN2012102654881 A CN 2012102654881A CN 201210265488 A CN201210265488 A CN 201210265488A CN 102757793 A CN102757793 A CN 102757793A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 110
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 125000003545 alkoxy group Chemical group 0.000 claims description 14
- 125000003342 alkenyl group Chemical group 0.000 claims description 12
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 11
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 4
- 125000004991 fluoroalkenyl group Chemical group 0.000 claims description 3
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 3
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 230000004044 response Effects 0.000 abstract description 4
- 230000003287 optical effect Effects 0.000 abstract description 3
- 239000012533 medium component Substances 0.000 abstract description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
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- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 18
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 16
- LHJSLDBKUGXPMI-UHFFFAOYSA-N tris(2-methylpropyl) borate Chemical compound CC(C)COB(OCC(C)C)OCC(C)C LHJSLDBKUGXPMI-UHFFFAOYSA-N 0.000 description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000306 component Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 5
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
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- 239000005457 ice water Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
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- YTXAYGAYACWVGD-UHFFFAOYSA-N palladium;hydrate Chemical compound O.[Pd] YTXAYGAYACWVGD-UHFFFAOYSA-N 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- RTORDUCHCUPSHB-UHFFFAOYSA-N Bc(ccc(-c1cc(CC(C2)C(C)CC)c2cc1)c1)c1F Chemical compound Bc(ccc(-c1cc(CC(C2)C(C)CC)c2cc1)c1)c1F RTORDUCHCUPSHB-UHFFFAOYSA-N 0.000 description 1
- 0 CCC(*)C(C1)Cc2c1ccc(-c(cc1)cc(F)c1-c1cc(F)ccc1)c2 Chemical compound CCC(*)C(C1)Cc2c1ccc(-c(cc1)cc(F)c1-c1cc(F)ccc1)c2 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- QDFKKJYEIFBEFC-UHFFFAOYSA-N Fc1cc(Br)ccc1 Chemical compound Fc1cc(Br)ccc1 QDFKKJYEIFBEFC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
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- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- Liquid Crystal Substances (AREA)
Abstract
The invention provides a compound with a general formula (I), which can be used as a liquid crystal medium component, and an application thereof. The compound has the characteristics of higher dielectric property and optical anisotropy; and a display using the compound can obtain higher response speed. The invention further provides a liquid crystal composition, which includes one or more of the compounds, and a liquid crystal display element, which includes the liquid crystal composition.
Description
Technical Field
The invention relates to compounds as components of liquid crystal media, to a method for the production thereof and to the use thereof.
Background
In liquid crystal displays, liquid crystals are used as dielectrics, the optical properties of which change reversibly under the action of an applied voltage. Electro-optic displays using liquid crystals as the medium are well known to those skilled in the art. These liquid crystal displays use various electro-optical effects. The most common are the TN (twisted nematic) effect, with a uniform, substantially planar initial alignment of the liquid crystal director and a nematic structure twisted by about 90 °, the STN (super twisted nematic) effect and the SBE (super twisted birefringence effect), with a nematic structure twisted by 180 ° or more.
The IPS (in-plane switching) effect, etc., which has recently increased in its application, enables the use of dielectrically positive and dielectrically negative liquid crystal media in a similar manner to "guest/host" displays, such in-plane switching modes (as DE4000451, DE0588568) being used in particular for LCDs of modern desktop monitors and being envisaged for display applications in multimedia applications.
Since in general the operating voltage of liquid-crystal displays should be as low as possible, since liquid-crystal media having a large absolute value of the dielectric anisotropy are used, these liquid-crystal media usually consist predominantly and in most cases even essentially of liquid-crystal compounds having a dielectric anisotropy of the corresponding sign, i.e. compounds of positive dielectric anisotropy in the case of dielectrically positive media and compounds of negative dielectric anisotropy in the case of dielectrically negative media. In the respective type of media (dielectrically positive or dielectrically negative), dielectrically neutral liquid-crystalline compounds are generally used in amounts of at most a significant amount. Liquid crystal compounds having a dielectric anisotropy of opposite sign to that of the medium are generally used little or not at all.
The prior art liquid crystal media generally have relatively high operating voltages and relatively long response times, which are inadequate, in particular, for image-forming displays. In addition, they are generally unsuitable for high operating temperatures and/or have inadequate low-temperature stability, and relatively unfavourable Δ n values, such as US6348244B, CN102153442, WO9919420, for which the Δ n is small.
To date, no known family of compounds having a liquid crystalline mesophase includes a single compound that satisfies all of these requirements. The development in the field of liquid crystal materials is still far and efforts are still being made to develop novel compounds capable of optimizing this type of display in order to improve the properties of the liquid crystal display elements.
Disclosure of Invention
The invention aims to provide a compound which can be used as a liquid crystal medium component.
It is another object of the present invention to provide a process for the preparation of said compounds.
It is still another object of the present invention to provide a liquid crystal composition comprising the compound.
It is still another object of the present invention to provide a liquid crystal display element comprising the liquid crystal composition as a constituent element.
In order to solve the above problems, the present invention provides the following technical solutions:
in one aspect of the present invention, there is provided a compound which can be used as a component of a liquid crystal medium, said compound having a structure represented by general formula (i):
wherein,
R1selected from the group consisting of H, halogen, halogenated or unsubstituted alkyl or alkoxy groups having 1 to 7 carbon atoms, unsubstituted alkenyl or alkenyloxy groups having 2 to 7 carbon atoms, wherein R is1One or more CH in2The radicals may be replaced independently of one another by-O-, -CF = CH-, -CF = CF-, -COO-or-O-CO-, and each two oxygen atoms are not linked to one another;
R2selected from H, Cl, CN, OCF3An alkyl or alkoxy group having 1 to 7 carbon atoms, an alkenyl or alkenyloxy group having 2 to 7 carbon atoms, a fluoroalkyl or fluoroalkoxy group having 1 to 4 carbon atoms and a fluoroalkenyl group having 2 to 4 carbon atoms;
L1～L12may be the same or different and are each independently H or F, wherein L is1～L12Up to six of which are F.
In some preferred embodiments, the R is1Selected from the group consisting of alkyl or alkoxy groups having 1 to 7 carbon atoms, alkenyl or alkenyloxy groups having 2 to 7 carbon atoms, wherein R is1One or more CH in2The radicals may be replaced independently of one another by-CF = CH-, -CF = CF-or-COO-.
In some preferred embodiments, the R is2Selected from the group consisting of H, OCF3Alkyl or alkoxy having 1 to 7 carbon atoms, alkenyl or alkenyloxy having 2 to 7 carbon atoms.
Preferably, the compound is selected from the group consisting of:
and
wherein R1 is selected from the group consisting of alkyl or alkoxy or alkenyl or alkenyloxy having 2-5 carbon atoms, and R2 is selected from the group consisting of OCF3, alkyl or alkoxy having 2-5 carbon atoms.
More preferably, the compound is selected from the group consisting of:
another aspect of the present invention provides a method for preparing the compound, comprising the steps of:
1) slowly dropwise adding n-butyllithium (n-BuLi, 2.4mol/L) to the compound of the formula a at the temperature of-65 to-70 ℃ under the protection of nitrogen
In a Tetrahydrofuran (THF) solution of the compound,
After the dripping reaction is finished for 2 hours, slowly dripping triisobutyl borate (triisobutyl borate) into the reaction system, and keeping the temperature at minus 65 to minus 70 ℃ to obtain a compound shown in the formula b;
2) Under the protection of nitrogen, sequentially reacting the compound of the formula b, the compound of the formula c,
(formula c)
Ethylene glycol dimethyl ether (DME), sodium carbonate (Na)2CO32mol/L), tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Placing in a eggplant-shaped bottle, slowly heating to 85 ℃ (± 2 ℃), and reacting for 2 hours to obtain a compound shown in a formula d;
3) Slowly dripping n-butyllithium (n-BuLi, 2.4mol/L) into a Tetrahydrofuran (THF) solution of the compound shown in the formula d at the temperature of-65 to-70 ℃ under the protection of nitrogen, reacting for 2 hours after dripping, slowly dripping triisobutyl borate (triisobutyl borate) into the reaction system, and keeping the temperature at the temperature of-65 to-70 ℃ to obtain the compound shown in the formula e;
(formula e)
4) Under the protection of nitrogen, sequentially reacting the compound of the formula e, the compound of the formula f,
(formula f)
Sodium carbonate (Na)2CO32mol/L), toluene, ethanol, water and tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) Placing the mixture into a three-neck flask, heating, stably refluxing for 6 hours, and stopping the reaction to obtain a compound shown in the formula g;
5) Slowly dripping n-butyllithium (n-BuLi, 2.4mol/L) into a Tetrahydrofuran (THF) solution of the compound shown in the formula g at the temperature of-65 to-70 ℃ under the protection of nitrogen, slowly dripping triisobutyl borate (triisobutyl borate) into the reaction system after dripping and keeping the temperature at the temperature of-65 to-70 ℃ for 1 hour, and naturally heating to-50 ℃ after dripping and keeping the temperature at the temperature of-65 to-70 ℃ for 1 hour to obtain the compound shown in the formula h;
5) Under the protection of nitrogen, sequentially reacting the compound of the formula h, the compound of the formula i,
Sodium carbonate (Na)2CO32mol/L), toluene, ethanol, water and tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) And (3) placing the mixture into a three-neck flask, heating, stopping heating after stable reflux is carried out for 6 hours, and cooling to 40-50 ℃ to obtain a compound (I).
Wherein:
R1selected from the group consisting of H, halogen, halogenated or unsubstituted alkyl or alkoxy groups having 1 to 7 carbon atoms, unsubstituted alkenyl or alkenyloxy groups having 2 to 7 carbon atoms, wherein R is1One or more CH in2The radicals may be replaced independently of one another by-O-, -CF = CH-, -CF = CF-, -COO-or-O-CO-, and each two oxygen atoms are not linked to one another;
R2selected from H, Cl, CN, OCF3An alkyl or alkoxy group having 1 to 7 carbon atoms, an alkenyl or alkenyloxy group having 2 to 7 carbon atoms, a fluoroalkyl or fluoroalkoxy group having 1 to 4 carbon atoms and a fluoroalkenyl group having 2 to 4 carbon atoms;
L1～L12may be the same or different and are each independently H or F, wherein L is1～L12Up to six of which are F.
It is a further aspect of the present invention to provide a liquid crystal composition comprising one or more of the compounds.
It is still another aspect of the present invention to provide a liquid crystal display element comprising the liquid crystal composition as a constituent element.
Compared with other liquid crystal compounds in the prior art, the liquid crystal compound of the general formula (I) has higher response speed and stable chemical properties; in the preparation process of the liquid crystal compound shown in the general formula (I), raw materials are easy to obtain, the synthetic route is simple and feasible, the liquid crystal compound is suitable for large-scale industrial production, is favorable for being used as a liquid crystal material for display, and can be used for improving the response time of a liquid crystal composition.
Drawings
FIG. 1 is a drawing of Compound I-2-11H NMR chart.
FIG. 2 is a drawing of compound I-4-51H NMR chart.
FIG. 3 is a drawing of Compound I-5-21H NMR chart.
Detailed Description
The invention will be illustrated below with reference to specific embodiments. It should be noted that the following examples are illustrative of the present invention, and are not intended to limit the present invention. Other combinations and various modifications within the spirit or scope of the present invention may be made without departing from the spirit or scope of the present invention.
The shorthand codes of the test items in the following examples are respectively expressed as:
cp (. degree. C.) clearing Point (nematic-isotropic phase transition temperature)
Δ n optical anisotropy (589 nm, 20 ℃ C.)
Delta epsilon dielectric anisotropy (1 KHz, 25 ℃ C.)
V90 saturation voltage = characteristic voltage at 90% relative contrast (normally white mode)
V10 threshold voltage = characteristic voltage at 10% relative contrast (normally white mode)
Wherein the refractive index anisotropy is measured by using an Abbe refractometer under a sodium lamp (589 nm) light source at 20 ℃; the dielectric test cell was of the type TN90, the cell thickness being 7 μm.
V10 test conditions: c/1KHZ, JTSB 7.0.
The reagents and other starting materials used in the present invention are commercially available.
Example 1
The synthetic route for preparing compound I-2-1 is shown below,
the specific process steps are as follows:
1) synthesis of Compound of formula 2
22.8g of the compound of formula 1 are dissolved in 200ml of Tetrahydrofuran (THF) solution, and the solution is cooled to-65 to-70 ℃ with ethanol and dry ice under nitrogen. 83.3ml of n-butyllithium (n-BuLi, 2.4mol/L) is slowly added dropwise into a Tetrahydrofuran (THF) solution of the compound of the formula 1, the solution is reacted for 2 hours after the dropwise addition, the solution turns from clear to yellow turbid, 92g of triisobutyl borate (triisobutyl borate) is continuously and slowly added dropwise into the reaction system, the temperature is kept at-65 to-70 ℃, and the solution turns from yellow turbid to colorless clear and then turns to white turbid.
The reaction was quenched with ice water, extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. Spin-drying the organic phase, adding petroleum ether, pulping, performing ultrasonic treatment, filtering, and pumping by an oil pump to obtain 12g of white solid, which is the compound of formula 2.
Mp：93.24~98.35℃；
MS m/z：158(M+)；
1H-NMR(d6-DMSO)δ：8.36(s,2H);6.53~7.45(m,3H)。
2) Synthesis of Compound of formula 4
In a 500ml eggplant-shaped bottle were charged 7.9g of the compound of formula 2, 11.25g of the compound of formula 3, 100ml of ethylene glycol dimethyl ether (DME), 50ml of sodium carbonate (Na)2CO3，2mol/L) 0.6g of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) The temperature was slowly raised to 85 ℃ (± 2 ℃) under nitrogen for 2 hours.
The reaction was quenched with water, extracted with ethyl acetate, washed with water, washed with a small amount of saturated brine, dried over anhydrous sodium sulfate for 1 hour, filtered, concentrated, column chromatographed (petroleum ether eluted), and spin dried to give 10.2g of a colorless oil, which is a compound of formula 4.
MS m/z：258(M+)
3) Synthesis of Compound of formula 5
22.8g of the compound of formula 4 are dissolved in 30ml of Tetrahydrofuran (THF) solution, and the solution is cooled to-65 to-70 ℃ with ethanol and dry ice under nitrogen protection. 6.25ml of n-butyllithium (n-BuLi, 2.4mol/L) is slowly dropped into a Tetrahydrofuran (THF) solution of the compound of formula 4, the solution is reacted for 2 hours after dropping, the solution is changed from orange red to orange yellow, 7.9g of triisobutyl borate (triisobutyl borate) is continuously and slowly dropped into the reaction system, the temperature is kept at-65 to-70 ℃, and the solution is changed from orange yellow to light yellow until colorless.
The reaction was quenched with ice water, extracted with ethyl acetate, washed with water, washed with saturated brine, dried over anhydrous sodium sulfate, and filtered. Spin-drying the organic phase, adding petroleum ether, pulping, performing ultrasonic treatment, filtering, and pumping by an oil pump to obtain 2g of a white solid, which is a compound of formula 5.
MS m/z：302(M+)；
1H-NMR(d6-DMSO)δ：8.34~8.39(d,2H);7.18~7.39(m,5H);2.97~3.06(m,2H);2.48~2.59(m,2H);2.27~2.37(m,1H);1.42~1.49(m,2H);0.90~0.95(t,3H)。
4) Synthesis of Compound I-2-1
A50 ml eggplant-shaped bottle was charged with 1.09g of the compound of formula 5, 0.97g of the compound of formula 6, 20ml of ethylene glycol dimethyl ether (DME), and 3ml of sodium carbonate (Na)2CO32mol/L), 0.6g of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) The temperature was slowly raised to 85 ℃ (± 2 ℃) under nitrogen for 2 hours.
Quenching the reaction with water, extracting with ethyl acetate, washing with water, washing with a small amount of saturated salt solution, drying with anhydrous sodium sulfate for 1 hour, filtering, concentrating, performing column chromatography, spin-drying purple fluorescent dots, pumping with an oil pump, recrystallizing with ethanol and petroleum ether, and pump-filtering to obtain needle-like white crystals 0.53g, and performing secondary crystallization to obtain crystals 0.35g, thereby obtaining the compound I-2-1.
MS m/z：452(M+)。
The nuclear magnetic resonance spectrum of the compound I-2-1 is1H-NMR(CDCl3)δ：7.24~7.73(m,13H);3.08~3.18(m,2H);2.43~2.72(m,5H);1.54~1.76(m,4H);0.99~1.05(m,6H)。
Liquid crystalline Properties of Compound I-2-1:
Δn:0.32Mp：122.2℃；Cp:246.7℃
process for preparation of compound I-2-11The H NMR chart is shown in FIG. 1.
Compounds of the following structural formula were prepared analogously:
example 2
The synthetic route for the preparation of compound I-4-5 is shown below,
the specific process steps are as follows:
1) preparation of the Compound of formula 8 by Process steps 1) to 3) of example 1
2) Synthesis of Compound of formula 9
A2000 ml three-necked flask was charged with 60g of the compound of formula 7, 112.4g of the compound of formula 8, 72.7g of sodium carbonate, 4g of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) 600ml of toluene, 300ml of ethanol, 300ml of water and nitrogen protection are carried out, heating is carried out, and the reaction is stopped after stable reflux is carried out for 6 hours. Pouring the reaction solution into water, separating, extracting, washing with water, evaporating to remove the solvent, and purifying by column chromatography to obtain a white solid 77.8g, which is the compound of formula 9.
Theoretical yield: 115.88g actual yield: yield of 77.8 g: 67.2% GC: 95.96 percent
3) Synthesis of Compound of formula 10
(formula 10)
A1000 ml three-neck flask is added with 33.8g of the compound of the formula 9, 300ml of Tetrahydrofuran (THF), 11g of potassium tert-butoxide and nitrogen protection, cooled to-65 to-70 ℃ by low temperature, 50ml of n-butyllithium (n-BuLi, 2.4mol/L) is added dropwise, and the temperature is kept at-65 to-70 ℃ for 1 hour after the dropwise addition. Dropwise adding 30g of triisobutyl borate (triisobutyl borate) into the reaction system, keeping the temperature at-65 to-70 ℃ for 1 hour after dropwise adding, naturally heating to-50 ℃ (± 2 ℃), pouring the reaction solution into 500ml of water, acidifying, separating, extracting, washing with water, evaporating to remove the solvent, washing with 90-120 ℃ petroleum ether, and performing suction filtration to obtain 24g of a light yellow solid, namely the compound of the formula 10.
Theoretical yield: 38.2g actual yield: yield of 24 g: 62.8 percent
4) Synthesis of Compound I-4-5
A1000 ml three-necked flask was charged with 12.7g of the compound of formula 10, 7.3g of the compound of formula 11, 7.8g of sodium carbonate, 0.4g of tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) 200ml of toluene, 100ml of ethanol, 100ml of water and nitrogen protection, heating the reaction, and stopping the reaction after stable reflux for 6 hours. And pouring the reaction solution into 500ml of water, separating the solution, extracting, washing with water, evaporating to remove the solvent, and purifying by column chromatography to obtain 7.5g of white solid, thus obtaining the compound I-4-5.
Theoretical yield: 15.16g actual yield: 7.5g yield: 49.67 percent
GC：98.86% DSC：C89.3N233.5I
Liquid Crystal Properties of Compound I-4-5:
Δn:0.30
process for preparation of compounds I-4-51The H NMR chart is shown in FIG. 2.
Compounds of the following structural formula were prepared analogously:
DSC：C86.6N217.3I Δn:0.30
example 3
The synthetic route for preparing compound I-5-2 is shown below,
the specific process steps are as follows:
1) preparation of the Compound of formula 13 by Process steps 1) to 3) of example 1
2) Synthesis of Compounds of formula 14
(formula 12)
A1000 ml three-necked flask was charged with 56.6g of the compound of formula 12, 59.6g of the compound of formula 13, 42.4g of sodium carbonate, 300ml of toluene, 200ml of ethanol, 200ml of water, and under nitrogen, 2.3g of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4) Heating, stably refluxing for 6 hours, stopping reaction, separating liquid, extracting, washing with water, evaporating to remove the solvent, and purifying by column chromatography to obtain 70g of a white solid which is the compound of formula 14.
GC: 99.8% theoretical yield: 81.8g, actual yield: 70g, yield: 85 percent of
3) Synthesis of Compound of formula 15
(formula 15)
Adding 70g of the compound shown in the formula 14 and 200ml of Tetrahydrofuran (THF) into a 500ml three-neck flask, cooling to-73 to-78 ℃ under the protection of nitrogen, dropwise adding 84ml of n-butyllithium (n-BuLi, 2.4mol/L), keeping the temperature at-73 to-78 ℃ for 1 hour after dropwise adding, then dropwise adding 51g of triisobutyl borate (triisobutyl borate) into the reaction system, keeping the temperature at-73 to-78 ℃ for 1 hour after dropwise adding, naturally heating to-50 ℃ (-2 ℃), slowly pouring the reaction liquid into 500ml of water, acidifying, separating, evaporating the solvent, washing with 90-120 ℃ petroleum ether, and performing suction filtration to obtain 51g of a white solid, namely the compound shown in the formula 15.
Theoretical yield: 64 g. Actual yield: 51 g. Yield: 80 percent of
4) Synthesis of Compound I-5-2
A500 ml three-necked flask was charged with 51g of the compound of formula 15, 40.7g of the compound of formula 16, 29.8g of sodium carbonate, 150ml of toluene, 75ml of ethanol, 150ml of water, under nitrogen, and 1.5g of tetrakis (triphenylphosphine) palladium (Pd (PPh) was added3)4) Heating, and stopping heating after stable reflux for 6 hours. And slowly pouring the reaction solution into 150ml of water, separating the liquid, extracting, washing with water, evaporating to remove the solvent, and purifying by column chromatography to obtain 60g of white solid, namely the compound I-5-2.
Theoretical yield: 70.4g, actual yield: 60g, yield: 85 percent.
DSC：C148.8S223.7N232.9
Liquid Crystal Properties of Compound I-5-2:
Δn:0.26 Δε:16.3
of the Compound I-5-21The HNMR map is shown in FIG. 3.
Compounds of the following structural formula were prepared analogously:
DSC：C138S185.2N236.7 Δn:0.266 Δε:13.8
example 4
Preparation of liquid Crystal composition
For convenience of expression, the following liquid crystal compounds are represented by the codes listed in Table 1:
TABLE 1 radical structural code of liquid crystal compounds
Take the following structure as an example:
the structure is represented by the code in table 1: it may be denoted as 3PTWTP3, again as:
it can be expressed as nCPTPOm, where n in the code represents the number of C atoms of the left alkyl group, e.g., n is "3", i.e., the alkyl group is-C3H7(ii) a C in the code represents cyclohexane; o in the code represents an oxygen atom; p in the code represents phenylene; in the code, m represents the number of C atoms in the alkyl group at the right end, for example, m is "1", that is, the alkyl group at the right end is-CH3。
Liquid crystal compositions were prepared with the components listed in table 2. Of these, 3IGGP3 and 3IGPUOCF3 were derived from examples 2 and 3, respectively, and the other individual components were known or their preparation methods could be easily derived from the prior art by those skilled in the relevant art, since they are based on standard procedures described in the literature.
The liquid crystal composition of the present invention can be prepared in a conventional manner. In general, the components of which the content is smaller are dissolved at a suitable elevated temperature in the main component of which the content is greater, or the components are mixed in an organic solvent, such as acetone, chloroform or methanol, and after thorough mixing the solvent is removed, for example by distillation.
TABLE 2 liquid crystal compositions and weight percentages of components thereof
| Components of liquid crystal composition | Weight percentage of each component (%) |
| |
6 |
| |
6 |
| |
8 |
| |
8 |
| |
6 |
| 3CCV | 44 |
[0181]
| |
5 |
| |
5 |
| |
6 |
| |
3 |
| |
3 |
The liquid crystal composition has the following measured properties:
Δn：0.114
Δε：3.08
CP：78
V90:3.284。
Claims (7)
1. A compound having the general formula (I):
wherein,
R1selected from the group consisting of H, halogen, halogenated or unsubstituted alkyl or alkoxy groups having 1 to 7 carbon atoms, unsubstituted alkenyl or alkenyloxy groups having 2 to 7 carbon atoms, wherein R is1One or more ofMultiple CH2The radicals may be replaced independently of one another by-O-, -CF = CH-, -CF = CF-, -COO-or-O-CO-, and each two oxygen atoms are not linked to one another;
R2selected from H, Cl, CN, OCF3An alkyl or alkoxy group having 1 to 7 carbon atoms, an alkenyl or alkenyloxy group having 2 to 7 carbon atoms, a fluoroalkyl or fluoroalkoxy group having 1 to 4 carbon atoms and a fluoroalkenyl group having 2 to 4 carbon atoms;
L1～L12may be the same or different and are each independently H or F, wherein L is1～L12Up to six of which are F.
2. A compound of claim 1, wherein R is1Selected from the group consisting of alkyl or alkoxy groups having 1 to 7 carbon atoms, alkenyl or alkenyloxy groups having 2 to 7 carbon atoms, wherein R is1One or more CH in2The radicals may be replaced independently of one another by-CF = CH-, -CF = CF-or-COO-.
3. A compound of claim 1, wherein R is2Selected from the group consisting of H, OCF3Alkyl or alkoxy having 1 to 7 carbon atoms, alkenyl or alkenyloxy having 2 to 7 carbon atoms.
4. A compound according to claims 1-3, wherein the compound is selected from the group consisting of:
wherein, R is1Selected from the group consisting of alkyl or alkoxy or alkenyl or alkenyloxy having 2 to 5 carbon atoms, said R2Selected from the group consisting of OCF3Alkyl or alkoxy having 2 to 5 carbon atoms.
5. The compound of claim 4, wherein the compound is selected from the group consisting of:
and
6. a liquid crystal composition comprising the liquid crystal compound according to any one of claims 1 to 5.
7. A liquid crystal display element comprising the liquid crystal composition according to claim 6.
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Cited By (4)
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| CN104673324A (en) * | 2013-11-27 | 2015-06-03 | 江苏和成光电科技有限公司 | Liquid crystal composition and display device comprising liquid crystal composition |
| TWI487779B (en) * | 2013-12-31 | 2015-06-11 | Daxin Materials Corp | Liquid crystal composition and liquid crystal display device |
| US9598639B2 (en) | 2014-07-23 | 2017-03-21 | Daxin Materials Corporation | Liquid-crystal compound, liquid-crystal composition and liquid-crystal display device |
| CN107828426A (en) * | 2013-05-13 | 2018-03-23 | 达兴材料股份有限公司 | Liquid crystal medium and liquid crystal display device |
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