CN116003361A - Liquid crystal compound, composition and application - Google Patents
Liquid crystal compound, composition and application Download PDFInfo
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- CN116003361A CN116003361A CN202211729502.9A CN202211729502A CN116003361A CN 116003361 A CN116003361 A CN 116003361A CN 202211729502 A CN202211729502 A CN 202211729502A CN 116003361 A CN116003361 A CN 116003361A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 86
- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- 239000000203 mixture Substances 0.000 title claims abstract description 37
- -1 4-cyclohexyl Chemical group 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000000000 cycloalkoxy group Chemical group 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000013078 crystal Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- APEHSYGALPMZGD-UHFFFAOYSA-N 1-bromo-2-cyclohexyl-3-propylbenzene Chemical compound C(CC)C=1C(=C(C=CC1)Br)C1CCCCC1 APEHSYGALPMZGD-UHFFFAOYSA-N 0.000 description 1
- BXGYYDRIMBPOMN-UHFFFAOYSA-N 2-(hydroxymethoxy)ethoxymethanol Chemical compound OCOCCOCO BXGYYDRIMBPOMN-UHFFFAOYSA-N 0.000 description 1
- RQDKJGHBCCKMIH-UHFFFAOYSA-N 2-bromo-6-fluoro-5,6-dimethylcyclohexa-1,3-diene Chemical group BrC1=CC(C(C=C1)C)(F)C RQDKJGHBCCKMIH-UHFFFAOYSA-N 0.000 description 1
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- VVWRJUBEIPHGQF-MDZDMXLPSA-N propan-2-yl (ne)-n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)\N=N\C(=O)OC(C)C VVWRJUBEIPHGQF-MDZDMXLPSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Landscapes
- Liquid Crystal Substances (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of liquid crystal compounds, in particular to a novel liquid crystal compound and application thereof. The liquid crystal compound provided by the invention has a structure shown in a general formula (I), has the characteristics of low rotational viscosity, large dielectric anisotropy, good intersolubility and stable performance in performance, can further improve the dielectric anisotropy of the conventional liquid crystal composition after being applied to the composition, and has the technical effect of reducing the driving voltage of a liquid crystal display device.
Description
Technical Field
The invention relates to the technical field of liquid crystal materials, in particular to a novel liquid crystal compound, and also relates to a composition comprising the liquid crystal compound and application thereof.
Background
Liquid crystal compounds have been widely used in the production of liquid crystal display devices for electronic computers, various measuring instruments, automobile instrument panels, electronic notebooks, cellular phones, computers, televisions, and the like, because of their inherent characteristics of optical anisotropy (Δn) and dielectric anisotropy (Δε), and their application ranges are expanding year by year. Liquid crystal mixtures are classified into dynamic scattering type (DS type), guest-host type (GH type), twisted nematic type (TN type), super twisted nematic type (STN type), thin film transistor type (TFT type), ferroelectric type (FLC) and the like according to the liquid crystal display mode. Liquid crystal compositions composed of liquid crystal compounds have been widely used as an important display material for manufacturing liquid crystal displays because of their excellent optical anisotropy and electrical anisotropy, and their electric field control, and low power consumption. With the mature use of thin film transistor technology, liquid crystal display devices are gradually beginning to be applied to the fields of mobile phones, televisions and the like closely related to life of people.
At present, the technology of TFT-LCD products is mature, the technical problems of visual angle, resolution, color saturation, brightness and the like are successfully solved, and the display performance of the TFT-LCD products is close to or exceeds that of CRT displays. Large-sized and medium-sized TFT-LCD displays have gradually taken up the mainstream position of flat panel displays in respective fields. However, the TFT-LCD still has many defects such as insufficient response, insufficient voltage, insufficient charge retention, etc. due to the limitations of the existing liquid crystal materials. Therefore, the search for single crystal compounds with low viscosity and high dielectric anisotropy is still an important research topic.
Disclosure of Invention
The invention aims to develop a novel liquid crystal compound which has the characteristics of low rotational viscosity, large dielectric anisotropy, good intersolubility and stable performance.
In a first aspect, the present invention provides a liquid crystal compound comprising a structure of formula (I):
wherein:
r is selected from H, unsubstituted or substituted alkyl, alkenyl, alkoxy, cycloalkyl or cycloalkoxy containing 1 to 12 carbon atoms; the substitution means that one or more of alkyl, alkenyl, alkoxy, cycloalkyl or cycloalkoxy groups containing 1 to 12 carbon atoms are-CH 2 The radicals are each independently of one another replaced by-C.ident.C-, -CF 2 O-, -ch=ch-, -O-, -CO-O-, or-O-CO-being substituted in such a manner that the O atoms are not directly bonded to each other, and wherein one or more H may be substituted by halogen;
ring A and ring B each independently represent 1, 4-cyclohexyl, 1, 4-phenyl or 1, 4-cyclohexenylene; wherein C on the 1, 4-cyclohexyl group may each independently be substituted with one or more O's, and H on the 1, 4-phenyl group may each independently be substituted with one or more halogen's; m, n are each independently 0,1 or 2;
Z 1 、Z 2 each independently represents a single bond, a double bond, an oxygen atom, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -，-CF 2 O-、-OCF 2 -or-ch=ch-.
As an embodiment of the present invention, in the general formula (1), the R is selected from an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, an alkenyl group, an alkoxy group, a cycloalkyl group or a cycloalkoxy group;
the substitution means that one or more of alkyl, alkenyl, alkoxy, cycloalkyl or cycloalkoxy groups containing 1 to 5 carbon atoms are-CH 2 The radicals are each independently of one another replaced by-C.ident.C-, -CF 2 O-, -ch=ch-, -O-, -CO-O-, or-O-CO-is substituted in such a manner that the O atoms are not directly bonded to each other, and wherein one or more H may be substituted with halogen.
As one embodiment of the present invention, in the general formula (1), the R is selected from alkyl or alkoxy groups having 1 to 5 carbon atoms.
Preferably, in formula (1), said R is selected from alkyl groups containing 2 to 5 carbon atoms.
As an embodiment of the present invention, in the general formula (1), the Z 1 、Z 2 Each independently represents a single bond or-CF 2 O-。
Preferably, said Z 1 Represents a single bond, Z 2 Represents a single bond or-CF 2 O-。
As one embodiment of the present invention, the liquid crystal compound comprises a structure represented by any one of the general formulae I-1-1 to I-1-16 and general formulae II-1-1 to II-1-16:
wherein, in the general formulas I-1-1 to I-1-16 and II-1-16, R is selected from alkyl groups containing 2 to 5 carbon atoms.
Preferably, R is ethyl, propyl, butyl or pentyl in the general formulae I-1-1 to I-1-16 and II-1-16.
As an embodiment of the present invention, the liquid crystal compound is selected from any one of the following structures:
in a second aspect, the present invention provides a liquid crystal material composition comprising a liquid crystal compound according to the present invention.
Preferably, the mass percentage of the liquid crystal compound in the composition is 1 to 80%, more preferably 3 to 50%, and still more preferably 10 to 20%.
In a third aspect, the present invention provides the use of said liquid crystal compound or said liquid crystal material composition in the field of liquid phase displays.
As a preferred embodiment, the present invention provides the use of the liquid crystal compound of the present invention or the liquid crystal material composition in a liquid phase display device.
Preferably, the liquid crystal display device includes, but is not limited to, a TN, ADS, FFS, IPS liquid crystal display.
The invention provides a novel liquid crystal compound, which has the characteristics of low rotational viscosity, large dielectric anisotropy, good intersolubility and stable performance in performance, can further improve the dielectric anisotropy of the conventional liquid crystal composition after being applied to the composition, and has the technical effect of reducing the driving voltage of a liquid crystal display device.
Detailed Description
The technical scheme of the invention is described in detail below. The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The starting materials are available from published commercial sources unless otherwise specified.
It should be noted that, according to the conventional detection method in the art, each performance parameter of the liquid crystal compound is obtained by linear fitting, where the specific meaning of each performance parameter is as follows:
delta epsilon represents the dielectric anisotropy at 25 ℃ and 1 kHz;
γ1 represents the rotational viscosity (mPas) at 25 ℃.
Δn is optical anisotropy (25 ℃);
c.p is the clearing point (. Degree. C.) of the liquid crystal composition;
VHR charge retention (%): the mixed liquid crystal is injected into a liquid crystal box, the liquid crystal box is placed into an incubator, after the temperature is stable, a test program is entered, a point is manually taken to obtain a charge retention rate value, the measurement voltage is 5V, the power-on Time is 5ms, and the retention Time (Holding Time) is 500ms.
The present invention is not limited to the preparation method. For example, the compounds provided by the present invention can be synthesized by the following several routes.
Route 1:
route 2:
route 3:
according to the above synthetic route, the person skilled in the art can perform the synthesis by using known common means, such as further selecting a suitable catalyst, solvent, determining a suitable reaction temperature, time, material ratio, etc., which is not particularly limited in the present invention. Unless otherwise indicated, starting materials for solvents, catalysts, bases, etc. used in the preparation process may be synthesized by published commercial routes or by methods known in the art.
The intermediates used in the above synthetic routes can be synthesized by the following methods.
The synthesis route of the main intermediate is as follows:
the specific synthesis steps are as follows:
1) Synthesis of 2-fluoro-4-bromophthalic acid
203g of 2-fluoro-4-bromo-o-xylene and 347g of potassium permanganate are added into a 500ml dry and clean three-necked flask, 275g of sulfuric acid with the mass ratio concentration of 80% are added, and the mixture is stirred and heated to 60 ℃ for reaction for 4 hours. 120g of sodium hydroxide and 300ml of water are added into the reaction solution, the aqueous phase hydrochloric acid is acidified to obtain a product, and petroleum ether is recrystallized to obtain 184g of 2-fluoro-4-bromo-phthalic acid, and the yield is 70%.
2) Synthesis of 2-fluoro-4-bromo-o-dimethanol
To a 1000ml dry and clean three-necked flask, 171g of 2-fluoro-4-bromophthalic acid, 40.5g of potassium borohydride, 78g of zinc chloride and 600ml of tetrahydrofuran were placed, and the mixture was heated to 60℃to 70℃with stirring and reacted for 6 hours. Slowly pouring 500ml of 2M hydrochloric acid aqueous solution at the temperature of minus 5 ℃ for acidification, extracting 500ml of toluene, washing with water to be neutral, and spin-drying the reaction liquid to obtain the compound 2-fluoro-4-bromo-o-dimethanol, 129g, and the yield is 85%.
3) Synthesis of 6-bromo-4-fluoro-1, 3-dihydroisobenzofuran
118g of 2-fluoro-4-bromophthalic dimethanol, 134g of triphenylphosphine, 600ml of tetrahydrofuran and 132g of DIAD were added dropwise to a 1000ml dry and clean three-necked flask at a temperature of 20℃to 30℃and reacted for 3 hours. Petroleum ether 500ml extraction, spin drying reaction liquid, reduced pressure distillation, obtaining compound 6-bromo-4-fluoro-1, 3-dihydro isobenzofuran, 97.7g, yield 90%.
4) Synthesis of (7-fluoro-1, 3-dihydroisobenzofuran-5-yl) boronic acid
To 1000ml of the dry and clean three-necked flask, 12g of magnesium turnings, 1ml of bromoethane and 100ml of tetrahydrofuran are added, the temperature is increased to initiate the reaction, 90g of 6-bromo-4-fluoro-1, 3-dihydroisobenzofuran and 200ml of tetrahydrofuran solution are added dropwise at the temperature of 40-50 ℃ for reaction for 1 hour. 94g of triisopropyl borate is added into another reaction bottle, the temperature is reduced to minus 40 ℃ to minus 50 ℃, and the Grignard reagent is slowly added into the triisopropyl borate for reaction for 3 hours. Acidifying with hydrochloric acid, extracting with ethyl acetate, spin-drying the reaction solution, and pulping with petroleum ether to obtain compound (7-fluoro-1, 3-dihydroisobenzofuran-5-yl) boric acid, 64g, and yield 85%.
5) Synthesis of 7-fluoro-1, 3-dihydroisobenzofuran-5-ol
60g (7-fluoro-1, 3-dihydroisobenzofuran-5-yl) boric acid, 42g 30% hydrogen peroxide and 200ml tetrahydrofuran are added into a 500ml dry and clean three-port bottle, and the temperature is controlled between 50 ℃ and 60 ℃ for reaction for 3 hours. Petroleum ether 500ml extraction, spin drying reaction liquid, reduced pressure distillation, obtaining compound 7-fluoro-1, 3-dihydro isobenzofuran-5-alcohol, 45.7g, yield 90%. Product MS (m/z): 154 (M+).
Example 1
The structural formula of the liquid crystal compound prepared in this example is:
the synthetic route is as follows:
the specific synthesis steps are as follows:
into a 1L three-necked flask, propylcyclohexylbromobenzene (28.0 g,0.1 mol), (7-fluoro-1, 3-dihydroisobenzofuran-5-yl) boric acid (18.2 g,0.1 mol), sodium carbonate (21.2 g,0.2 mol), toluene 150mL, ethanol 150mL and water 150mL were charged, and Pd (PPh) was added after the reaction system was replaced with nitrogen for protection 3 ) 4 (11.5 g,0.01 mol). The reaction was heated at reflux for 4 hours and stopped. Evaporating off the solvent, extracting with dichloromethane, drying with anhydrous magnesium sulfate, filtering, subjecting to ethyl acetate column chromatography, and spin-drying to obtain 29.1g white solid LC-01, 86% yield.
Product MS (m/z): 338 (m+); DSC:88.3 ℃; Δn is 0.131, Δε is 8.9, and γ1 is 84 mPa.s.
1 H-NMR(CDCl 3 ,300MHz)δH：0.90-2.60(m,17H),3.50-4.60(m,4H),6.50-7.60(m,6H)。
Example 2
The structural formula of the liquid crystal compound prepared in this example is:
the synthetic route is as follows:
the specific synthesis steps are as follows:
(1) Under the protection of nitrogen, adding (95.0 g,0.44 mol) 6-bromo-4-fluoro-1, 3-dihydroisobenzofuran and 250ml tetrahydrofuran into a 2L reaction bottle, dropwise adding 0.48mol n-hexane solution of n-butyllithium at the temperature of-75 to-85 ℃, carrying out heat preservation reaction for 1 hour after dropwise adding, dropwise adding a solution consisting of (81.4 g,0.37 mol) propyl dicyclohexylketone and 100ml tetrahydrofuran at the temperature of-75 to-85 ℃, and then naturally returning to the temperature of-30 ℃. Adding 300ml of water for quenching reaction, and performing conventional post-treatment to obtain 109.2g of light yellow solid compound LC-02-M1 with the yield of 82%;
(2) Into the reaction flask was charged (108.0 g,0.3 mol) of LC-02-M1, (5.6 g,0.03 mol) of p-toluenesulfonic acid, 0.1g of 2, 6-di-t-butyl-p-cresol and 200ml of toluene, and the mixture was reacted under reflux for 8 hours. Conventional work-up gave 87.2g of LC-02-M2 as a white solid in 85% yield.
(3) LC-02-M2 (171 g,0.5 mol), 17g palladium on carbon (50% water content), 340mL toluene, 170mL ethanol, and hydrogen were added to the hydrogenation reactor, the reaction was monitored for 5 hours until no starting material remained, the palladium on carbon was filtered, the solvent was distilled off, 300mL ethanol+150 mL heptane was recrystallized, and suction filtration and drying were performed to obtain 77.4g white solid LC-02 with a yield of 45%.
Product(s)MS (m/z): 344 (m+); DSC:93.4 ℃; Δn is 0.092, Δε is 8.4, and γ1 is 92 mPas. 1 H-NMR(CDCl 3 ,300MHz)：δH:0.90-2.60(m,27H),3.50-4.60(m,4H),6.50-7.60(m,2H)。
Example 3
The structural formula of the liquid crystal compound prepared in this example is:
the synthetic route is as follows:
the specific synthesis steps are as follows:
(1) Propylphenyl-3, 5-difluorobenzene (116.0 g,0.5 mol), 1L tetrahydrofuran are added into a 2L three-port bottle, stirring is started until the solid is completely dissolved, nitrogen is pumped and discharged three times, the temperature is reduced to-70 ℃, 232mL of 2.5M n-butyllithium is dropwise added at the temperature of-65 ℃ to-75 ℃, after the dropwise addition, a dropping funnel is flushed with 100mL of tetrahydrofuran, the temperature is controlled to-65 ℃ to-75 ℃ for 1 hour, 0.5L of tetrahydrofuran solution containing 141g of difluoromethane is dropwise added at the temperature of-65 ℃ to-75 ℃, after the dropwise addition, and the temperature is naturally raised to-20 ℃. And (3) dripping a solution consisting of 40ml of concentrated hydrochloric acid and 200ml of water into the reaction solution, stirring for 30 minutes, standing to separate out a water phase, adding 0.5L of petroleum ether, washing with 1L multiplied by 3 water for three times, spin-drying the solvent, recrystallizing with ethanol, filtering and drying to obtain 158.4g of white solid LC-03-M1, wherein the yield is 68%.
(2) Into a 1L three-necked flask, compound LC-03-M1 (37.8 g,0.105 mol), 200mL of DMF was added, stirring was started, and compound 7-fluoro-1, 3-dihydroisobenzofuran-5-ol (15.4 g,0.1 mol), potassium carbonate (19.3 g,0.14 mol) was added, nitrogen was purged three times, heated to raise the temperature, and the temperature was controlled to 90-95℃for reaction for 5 hours. 150mL of toluene is added to the reaction solution for extraction, the mixture is washed to be neutral by water, the solvent is dried by spin, and petroleum ether ethanol is recrystallized to obtain 38.2g of white solid LC-03, and the yield is 88%.
Product MS (m/z): 434 (m+); DSC:52.6 ℃; Δn is 0.185, Δε is 26.5, and γ1 is 120 mPa.s.
1 H-NMR(CDCl 3 ,300MHz)：δH:0.90-2.60(m,7H),3.50-4.60(m,4H),6.50-7.60(m,8H)。
Example 4
The structural formula of the liquid crystal compound prepared in this example is:
the synthetic route is as follows:
the 2',3, 5-trifluoro-4' -propyl-1, 1',4' -terphenyl was used instead of propylphenyl-3, 5-difluorobenzene and the appropriate material ratio was chosen, the other materials and steps were the same as in example 3, giving 38.0g of a white solid with a yield of about 72%.
Product MS (m/z): 528 (m+); DSC:87.3 ℃; Δn is 0.196, Δε is 29.4, and γ1 is 220 mPa.s.
1 H-NMR(CDCl 3 ,300MHz)：δH:0.90-2.60(m,7H),3.50-4.60(m,4H),6.50-7.60(m,11H)。
With reference to the synthetic schemes of examples 1 to 4, other liquid crystal compounds according to the present invention can be obtained stably and efficiently by simply replacing the corresponding raw materials without changing any substantial operation.
The liquid crystal compound can be used for preparing a liquid crystal composition. Wherein said liquid crystal compound is added in a reasonable manner in an amount of preferably 1 to 80%, preferably 3 to 50%, more preferably 10 to 20%. It is expected by those skilled in the art that the addition of the above liquid crystal compound can further improve the dielectric anisotropy of the conventional liquid crystal composition and has the technical effect of reducing the driving voltage of the device.
The liquid crystal compound and the liquid crystal composition provided by the invention can be applied to liquid crystal display devices, and the liquid crystal display devices comprise, but are not limited to, TN, ADS, FFS or IPS liquid crystal displays. After the liquid crystal composition is applied to a liquid crystal display device, the liquid crystal composition has the advantage of reducing the driving voltage.
The liquid crystal compounds prepared in examples 1 to 4 of the present invention were used for mixed crystal experiments, and various liquid crystal monomers in the following mixed crystal examples were synthesized by a known method or commercially available.
The liquid crystal compound and other liquid crystal monomers provided by the invention are adopted to prepare a mixed crystal composition, and the proportion of the components and the detection result are shown in the following table. The amounts of the components in the following examples are expressed in parts by weight (i.e., parts by weight).
Mixed Crystal example 1
The component proportions and detection results of the mixed crystal composition provided in this example are shown in table 1 below.
Table 1 weight parts of each component and performance parameters in liquid crystal compositions
Mixed crystal example 2
The component proportions and detection results of the mixed crystal composition provided in this example are shown in table 2 below.
Table 2 weight parts of each component and performance parameters in liquid crystal composition
Mixed crystal comparative example
The component proportions and the detection results of the mixed crystal composition provided in this comparative example are shown in Table 3 below.
TABLE 3 Performance parameters of liquid Crystal compositions without addition of Compounds of the invention
As can be seen from tables 1-3 above: the liquid crystal composition added with the compound has moderate rotational viscosity, moderate delta n value and high charge retention rate, and particularly has great dielectric anisotropy. The amount of the compound to be added is preferably 1 to 80%, more preferably 10 to 20%.
In addition to the compositions exemplified in the above mixed crystal examples, other liquid crystal compositions to which other liquid crystal compounds provided by the present invention are added can also obtain excellent optical and electrical properties.
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. A liquid crystal compound characterized by comprising a structure represented by the general formula (I):
wherein:
r is selected from H, unsubstituted or substituted alkyl, alkenyl, alkoxy, cycloalkyl or cycloalkoxy containing 1 to 12 carbon atoms; the substitution means that one or more of alkyl, alkenyl, alkoxy, cycloalkyl or cycloalkoxy groups containing 1 to 12 carbon atoms are-CH 2 The radicals are each independently of one another replaced by-C.ident.C-, -CF 2 O-, -CH=CH-, -O-, -CO-O-, or-O-CO-is substituted in such a manner that O atoms are not directly bonded to each other, andwherein one or more H may be substituted with halogen;
ring A and ring B each independently represent 1, 4-cyclohexyl, 1, 4-phenyl or 1, 4-cyclohexenylene; wherein C on the 1, 4-cyclohexyl group may each independently be substituted with one or more O's, and H on the 1, 4-phenyl group may each independently be substituted with one or more halogen's; m, n are each independently 0,1 or 2;
Z 1 、Z 2 each independently represents a single bond, a double bond, an oxygen atom, -CH 2 CH 2 -、-CH 2 O-、-OCH 2 -，-CF 2 O-、-OCF 2 -or-ch=ch-.
2. The liquid crystal compound according to claim 1, wherein R is selected from an unsubstituted or substituted alkyl group having 1 to 5 carbon atoms, alkenyl group, alkoxy group, cycloalkyl group or cycloalkoxy group; the substitution means that one or more of alkyl, alkenyl, alkoxy, cycloalkyl or cycloalkoxy groups containing 1 to 5 carbon atoms are-CH 2 The radicals are each independently of one another replaced by-C.ident.C-, -CF 2 O-, -ch=ch-, -O-, -CO-O-, or-O-CO-is substituted in such a manner that the O atoms are not directly bonded to each other, and wherein one or more H may be substituted with halogen.
3. A liquid crystal compound according to claim 1 or 2, wherein R is selected from alkyl or alkoxy groups containing 1-5 carbon atoms.
4. A liquid crystal compound according to any one of claims 1 to 3, wherein R is selected from alkyl groups containing 2 to 5 carbon atoms.
5. The liquid crystal compound according to any one of claims 1 to 4, wherein Z 1 、Z 2 Each independently represents a single bond or-CF 2 O-, preferably, the Z 1 Represents a single bond, Z 2 Represents a single bond or-CF 2 O-。
6. The liquid crystal compound according to any one of claims 1 to 5, wherein the liquid crystal compound comprises a structure represented by any one of the general formulae I-1-1 to I-1-16 and II-1-16:
wherein R is selected from alkyl groups containing 2-5 carbon atoms.
7. The liquid crystal compound according to any one of claims 1 to 6, wherein the liquid crystal compound is selected from any one of the following structures:
8. a liquid crystal material composition comprising the liquid crystal compound according to any one of claims 1 to 7; the mass percentage of the liquid crystal compound in the composition is 1-80%, preferably 3-50%, more preferably 10-20%.
9. Use of a liquid crystal compound according to any one of claims 1 to 7 or a liquid crystal material composition according to claim 8 in the field of liquid phase display.
10. Use of the liquid crystal compound according to any one of claims 1 to 7 or the liquid crystal material composition according to claim 8 in a liquid phase display device; preferably, the liquid crystal display device comprises a TN, ADS, FFS, IPS liquid crystal display.
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| CN116970405A (en) * | 2023-06-28 | 2023-10-31 | 北京燕化集联光电技术有限公司 | Liquid crystal compound, composition and application thereof |
| CN116987509A (en) * | 2023-06-30 | 2023-11-03 | 北京燕化集联光电技术有限公司 | Liquid crystal compound, composition and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264866A (en) * | 2008-12-22 | 2011-11-30 | 默克专利股份有限公司 | Liquid crystal display |
| CN104003964A (en) * | 2014-06-06 | 2014-08-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing tetrahydropyrane ring and application of Liquid crystal compound |
| CN104059674A (en) * | 2014-06-06 | 2014-09-24 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing difluoromethoxy bridged bond and application thereof |
| CN107267153A (en) * | 2016-04-08 | 2017-10-20 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds, composition and its application |
| CN111778040A (en) * | 2019-04-03 | 2020-10-16 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and preparation method and application thereof |
| CN114105941A (en) * | 2020-08-27 | 2022-03-01 | 北京八亿时空液晶科技股份有限公司 | Novel liquid crystal compound and preparation method and application thereof |
-
2022
- 2022-12-30 CN CN202211729502.9A patent/CN116003361B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102264866A (en) * | 2008-12-22 | 2011-11-30 | 默克专利股份有限公司 | Liquid crystal display |
| CN104003964A (en) * | 2014-06-06 | 2014-08-27 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing tetrahydropyrane ring and application of Liquid crystal compound |
| CN104059674A (en) * | 2014-06-06 | 2014-09-24 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal composition containing difluoromethoxy bridged bond and application thereof |
| CN107267153A (en) * | 2016-04-08 | 2017-10-20 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds, composition and its application |
| CN111778040A (en) * | 2019-04-03 | 2020-10-16 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound and preparation method and application thereof |
| CN114105941A (en) * | 2020-08-27 | 2022-03-01 | 北京八亿时空液晶科技股份有限公司 | Novel liquid crystal compound and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 杭德余等: "我国显示用液晶材料的研究进展", 《安徽化工》, no. 4, 31 August 2001 (2001-08-31), pages 2 - 4 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116970405A (en) * | 2023-06-28 | 2023-10-31 | 北京燕化集联光电技术有限公司 | Liquid crystal compound, composition and application thereof |
| CN116987509A (en) * | 2023-06-30 | 2023-11-03 | 北京燕化集联光电技术有限公司 | Liquid crystal compound, composition and application thereof |
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