CN113881443A - Liquid crystal compound containing dibenzothiophene structure and application thereof - Google Patents
Liquid crystal compound containing dibenzothiophene structure and application thereof Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 83
- 150000001875 compounds Chemical class 0.000 title claims abstract description 76
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 title claims abstract description 8
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 12
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000460 chlorine Chemical group 0.000 claims description 2
- 229910052801 chlorine Chemical group 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- RGOVYLWUIBMPGK-UHFFFAOYSA-N nonivamide Chemical compound CCCCCCCCC(=O)NCC1=CC=C(O)C(OC)=C1 RGOVYLWUIBMPGK-UHFFFAOYSA-N 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 230000003287 optical effect Effects 0.000 abstract description 6
- 230000004044 response Effects 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 230000003245 working effect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 238000012512 characterization method Methods 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000004587 chromatography analysis Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010626 work up procedure Methods 0.000 description 3
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- CYPYTURSJDMMMP-WVCUSYJESA-N (1e,4e)-1,5-diphenylpenta-1,4-dien-3-one;palladium Chemical compound [Pd].[Pd].C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1.C=1C=CC=CC=1\C=C\C(=O)\C=C\C1=CC=CC=C1 CYPYTURSJDMMMP-WVCUSYJESA-N 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 206010047571 Visual impairment Diseases 0.000 description 1
- 239000007805 chemical reaction reactant Substances 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
- C09K19/3491—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having sulfur as hetero atom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nonlinear Science (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention relates to the field of liquid crystal compounds and application thereof, in particular to a liquid crystal compound containing a dibenzothiophene structure and application thereof; the liquid crystal compound has a structure shown in a general formula I or a general formula II:
Description
Technical Field
The invention relates to the field of liquid crystal compounds and application thereof, in particular to a liquid crystal compound containing a dibenzothiophene structure and application thereof.
Background
The liquid crystal material has great research value and good application prospect when being used as an environmental material in the fields of information display materials, organic optoelectronic materials and the like. Liquid crystal materials have many advantages as novel display materials, such as extremely low power consumption, low driving voltage, and the like. Compared with other materials, the material also has the advantages of small volume, light weight, long service life, large display information amount, no electromagnetic radiation and the like, can almost meet the requirements of various information displays, and is particularly suitable for TFT-LCD (thin film transistor technology) products.
In the TFT active matrix system, there are mainly a TN (Twisted Nematic) mode, an IPS (In-Plane Switching) mode, an FFS (Fringe Field Switching) mode, a VA (Vertical Alignment) mode, and the like.
At present, the TFT-LCD product technology has matured, and successfully solves the technical problems of viewing angle, resolution, color saturation, brightness, etc., and large-size and medium-small-size TFT-LCD displays have gradually occupied the mainstream status of flat panel displays in respective fields. For a dynamic picture display application, in order to realize high quality display and eliminate afterimage and tailing of a display picture, a liquid crystal material is required to have a fast response speed, and thus the liquid crystal material is required to have a rotational viscosity γ 1 as low as possible. In addition, in order to reduce power consumption of the liquid crystal display device, it is necessary to reduce the driving voltage of the liquid crystal as much as possible, and thus it is required to improve the dielectric anisotropy Δ ∈ of the liquid crystal.
The liquid crystal material is used as a core functional material of a liquid crystal display device, and is required to have a wide variety of performance parameters, particularly the rotary viscosity gamma 1 of the liquid crystal material is reduced and the dielectric anisotropy delta epsilon of the liquid crystal material is improved in order to meet the requirements of various performance parameters of the liquid crystal display device and meet the process requirements of the liquid crystal display device. In order to improve the properties of materials and enable the materials to meet new requirements, the synthesis of novel structure liquid crystal compounds and the research of structure-property relationship become important work in the field of liquid crystal.
Disclosure of Invention
The invention aims to provide a liquid crystal compound containing a dibenzothiophene structure, so as to overcome the defects of the existing liquid crystal material and improve the application value of the liquid crystal compound.
The liquid crystal compound has a structure shown in a general formula I or a general formula II:
wherein R is1、R2Each independently represents-H, -Cl, -F, -CN, -OCN, -OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-SCN、-NCS、-SF5、C1-C15Alkyl of (C)1-C15Alkoxy group of (C)2-C15Alkenyl or C2-C15Alkenyloxy of (a); or, optionally containing-CH2One of-CH in the group2-or at least two non-adjacent-CHs2-substituted by-CH ═ CH-, -C ≡ C-, -COO-, -OOC-, cyclobutyl, cyclopropyl, -O-or-S-; or, at least one hydrogen of any of the above hydrogen-containing groups is substituted with fluorine or chlorine;
A1represents a single bond or one of the following groups:
A2represents a single bond or one of the following groups:
Z1、Z2each independently represents a single bond, -O-, -CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH＝CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-or-CF ═ CF —;
a. b independently of one another represents 0, 1 or 2.
As a further preferable technical solution, the liquid crystal compound is selected from one of the following compounds:
preferably, the liquid crystal compound is selected from one of the following compounds:
the second object of the present invention is to provide a method for preparing the liquid crystal compound.
Specifically, when the liquid crystal compound is a compound of the general formula I, the preparation method comprises the following steps:
1) to be provided with
And
as a raw material, through a Suzuki reaction to obtain
2)
Reacting with trifluoromethanesulfonic anhydride to obtain
3)
Reaction with ethyl mercaptopropionate to give
4)
Is subjected to base catalytic ring closure to obtain
Preferably, in the step 1),
and
the feeding molar ratio of (A) to (B) is 0.9-1.5: 1.0;
preferably, in the step 2),
the feeding molar ratio of the water to the trifluoromethanesulfonic anhydride is 0.1-0.3: 0.1 to 0.5;
as a preferable aspect of the above-mentioned technical means,in the step 3), the step of the method comprises the following steps,
the feeding molar ratio of the compound to the ethyl mercaptopropionate is 0.1-0.3: 0.1 to 0.3;
preferably, in the step 4),
the feeding molar ratio of the alkali to the alkali is 0.1-1.0: 1.0.
when the liquid crystal compound is a compound of the general formula II, the preparation method comprises the following steps:
1) to be provided with
And
as a raw material, through a Suzuki reaction to obtain
2)
Reacting with trifluoromethanesulfonic anhydride to obtain
3)
Reaction with ethyl mercaptopropionate to give
4)
Is subjected to base catalytic ring closure to obtain
Preferably, in the step 1),
and
the feeding molar ratio of (A) to (B) is 0.9-1.5: 1.0;
preferably, in the step 2),
the feeding molar ratio of the water to the trifluoromethanesulfonic anhydride is 0.1-0.3: 0.1 to 0.5;
preferably, in the step 3),
the feeding molar ratio of the compound to the ethyl mercaptopropionate is 0.1-0.3: 0.1 to 0.3;
preferably, in the step 4),
the feeding molar ratio of the alkali to the alkali is 0.1-1.0: 1.0.
the above reaction starting materials can be synthesized by publicly available commercial methods or by methods known per se in the literature.
The method of the invention, if necessary, involves conventional post-treatment, such as: extracting with dichloromethane, ethyl acetate or toluene, separating liquid, washing with water, drying, evaporating with vacuum rotary evaporator, and purifying the obtained product by vacuum distillation or recrystallization and/or chromatographic separation.
The liquid crystal compound can be stably and efficiently obtained by the preparation method.
The third object of the present invention is to provide a liquid crystal composition containing the above liquid crystal compound.
Preferably, in the above technical solution, the liquid crystal compound is 1 to 60% by mass of the liquid crystal composition; preferably 3-50%; more preferably 5 to 25%.
The fourth purpose of the invention is to provide the application of the liquid crystal compound and/or the liquid crystal composition in the field of liquid crystal display; preferably in liquid crystal display devices including, but not limited to, TN, ADS, VA, PSVA, FFS or IPS liquid crystal displays.
The liquid crystal compound provided by the invention has the chemical main structure of dibenzothiophene, the dielectric anisotropy of the structure is larger, the pyran group is introduced into the molecular structure of the liquid crystal compound provided by the invention, and fluorine atoms are introduced into the 4-position and the 6-position of the dibenzothiophene to form a strong synergistic effect, so that the negative dielectric anisotropy of the liquid crystal compound is extremely high, the clearing point is obviously improved, the optical anisotropy is higher, the rotational viscosity and the liquid crystal intersolubility are moderate, and the low-temperature working effect is excellent, and the performances in the aspects of good thermal stability, chemical stability, optical stability, mechanics and the like are good; therefore, the driving voltage is effectively reduced, the response speed of the liquid crystal display device is improved, and the liquid crystal display device has the characteristics of high charge retention rate and the like.
Detailed Description
The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
The starting materials are commercially available from the open literature unless otherwise specified.
According to the conventional detection method in the field, various performance parameters of the liquid crystal compound are obtained through linear fitting, wherein the specific meanings of the performance parameters are as follows:
Δ n represents optical anisotropy (25 ℃); Δ ε represents the dielectric anisotropy (25 ℃, 1000 Hz); γ 1 represents rotational viscosity (mpa.s, 25 ℃); cp stands for clearing point.
Example 1
A liquid crystal compound containing a dibenzothiophene structure has a structural formula as follows:
the synthetic route for the preparation of compound BYLC-01 is shown below:
the method comprises the following specific steps:
(1) synthesis of Compound BYLC-01-3:
under nitrogen protection, 46.8g (0.2mol) of the compound BYLC-01-1, 47.6g (0.2mol) of the compound BYLC-01-2, 400ml of toluene, 200ml of deionized water, 200ml of ethanol, 55.2g of anhydrous potassium carbonate, and 0.6g of palladium tetratriphenylphosphine were added to a reaction flask, and the mixture was heated under reflux for 12 hours. Conventional work-up was carried out, purification by chromatography and recrystallization from ethanol gave 62g of a white solid (compound BYLC-01-3), GC: 99.4%, yield: 89 percent;
(2) synthesis of Compound BYLC-01-4:
under the protection of nitrogen flow, 300mL of dichloromethane was added to the glass reaction flask, stirring was started, and 62g of BYLC-01-3 was added. Cooling to 0 ℃, adding 35.67g of pyridine and 2.75g of DMAP, controlling the temperature to be-15 to-10 ℃, and dropwise adding 86.5g of trifluoromethanesulfonic anhydride. After that, the temperature is controlled to be minus 10 ℃, and the mixture is stirred for 3 hours at the temperature of minus 10 to minus 5 ℃. Cooling to-10 deg.C, adding 100ml water, controlling temperature at 0-5 deg.C, stirring for 10min, standing for 10min, separating, washing organic layer with water for 100ml 3 times, mixing organic layers, adding 50g anhydrous sodium sulfate, drying, and spin-drying solvent;
heating 200ml ethanol to 80 ℃ for dissolution, naturally cooling to 17 ℃ under stirring, stirring at the temperature for 0.5h, and filtering by suction to obtain 68.4g of a compound BYLC-01-4, wherein the yield is 80 percent and the HPLC is 98.5 percent;
(3) synthesis of Compound BYLC-01-5:
57.64g (0.12mol) of BYLC-01-4, 19.3g of ethyl mercaptopropionate, 300ml of toluene, 33.1g of anhydrous potassium carbonate, 1.1g of tris (dibenzylideneacetone) dipalladium and 1.0g of 2-dicyclohexylphosphine-2 ', 6' -dimethoxybiphenyl were charged into a reaction flask under nitrogen protection, and the mixture was heated under reflux for 16 hours. Conventional work-up was carried out and purification by chromatography gave (compound BYLC-01-5)34.4g, GC: 93.1%, yield: 60 percent;
(4) synthesis of Compound BYLC-01:
under the protection of nitrogen, 23.9g (0.05mol) of compound BYLC-01-5, 100ml of N, N-dimethylformamide and 13.8g of anhydrous potassium carbonate were added to a reaction flask, and the temperature was controlled at 130 ℃ and 140 ℃ for reaction for 6 hours. Conventional work-up was carried out, purification by chromatography, elution with n-hexane and recrystallization with ethanol gave 13.2g of a white solid (compound BYLC-01), GC: 99.8%, yield: 77 percent.
The structural characterization information for compound BYLC-01 is as follows:
the obtained white solid BYLC-01 was analyzed by GC-MS and the M/z of the product was 344.0(M +).
Example 2
According to the technical scheme of the example 1, the following liquid crystal compounds can be synthesized by simply replacing corresponding raw materials without changing any substantial operation:
the structural characterization information for compound BYLC-02 is as follows:
the resulting white solid BYLC-02 was analyzed by GC-MS and the M/z of the product was 330.1(M +).
Example 3
According to the technical scheme of the example 1, the following liquid crystal compounds can be synthesized by simply replacing corresponding raw materials without changing any substantial operation:
the structural characterization information for compound BYLC-03 is as follows:
the resulting white solid BYLC-03 was analyzed by GC-MS and the M/z of the product was 316.0(M +).
Example 4
According to the technical scheme of the example 1, the following liquid crystal compounds can be synthesized by simply replacing corresponding raw materials without changing any substantial operation:
the structural characterization information for compound BYLC-04 is as follows:
the obtained white solid BYLC-04 was analyzed by GC-MS and the M/z of the product was 362.1(M +);
example 5
According to the technical scheme of the example 1, the following liquid crystal compounds can be synthesized by simply replacing corresponding raw materials without changing any substantial operation:
the structural characterization information for compound BYLC-05 is as follows:
the resulting white solid BYLC-05 was analyzed by GC-MS and the M/z of the product was 330.1(M +).
Example 6
According to the technical scheme of the example 1, the following liquid crystal compounds can be synthesized by simply replacing corresponding raw materials without changing any substantial operation:
the structural characterization information of compound BYLC-06 is as follows:
the resulting white solid BYLC-06 was analyzed by GC-MS and the M/z of the product was 358.1(M +).
Experimental example 1
The liquid crystal compounds BYLC-01, BYLC-02, BYLC-03, BYLC-04, BYLC-05 and BYLC-06 prepared in the examples 1 to 6 and the liquid crystal compound of the comparative example 1 (another known and common similar liquid crystal compound) are subjected to linear fitting according to a conventional detection method in the field to obtain various performance parameters of the liquid crystal compound, and the detection results are shown in Table 1:
table 1: results of Property measurement of liquid Crystal Compound
As is apparent from the detection results in table 1, compared with the conventional compound with a similar chemical structure, the liquid crystal compound provided by the present invention has a higher negative dielectric anisotropy Δ ∈ and a significantly higher clearing point Cp while maintaining a large optical anisotropy Δ n, a good rotational viscosity γ 1 and liquid crystal intersolubility, thereby effectively increasing the negative dielectric anisotropy of the liquid crystal composition, improving the response time, and increasing the operating temperature of the liquid crystal composition.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A liquid crystal compound containing a dibenzothiophene structure, which is characterized by having a structure shown in a general formula I or a general formula II:
wherein R is1、R2Each independently represents-H, -Cl, -F, -CN, -OCN, -OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-SCN、-NCS、-SF5、C1-C15Alkyl of (C)1-C15Alkoxy group of (C)2-C15Alkenyl or C2-C15Alkenyloxy of (a); or, optionally containing-CH2One of-CH in the group2-or at least two non-adjacent-CHs2-substituted by-CH ═ CH-, -C ≡ C-, -COO-, -OOC-, cyclobutyl, cyclopropyl, -O-or-S-; or, at least one hydrogen of any of the above hydrogen-containing groups is substituted with fluorine or chlorine;
A1represents a single bond or one of the following groups:
A2represents a single bond or one of the following groups:
Z1、Z2each independently represents a single bond, -O-, -CH2-、-CH2-CH2-、-(CH2)3-、-(CH2)4-、-CH＝CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-or-CF ═ CF —;
a. b independently of one another represents 0, 1 or 2.
2. The liquid crystal compound according to claim 1, wherein the liquid crystal compound is selected from one of the following compounds:
3. the liquid crystal compound according to claim 2, wherein the liquid crystal compound is selected from one of the following compounds:
4. a method for producing the liquid crystal compound according to any one of claims 1 to 3, comprising the steps of:
1) to be provided with
And
as a raw material, through a Suzuki reaction to obtain
2)
Reacting with trifluoromethanesulfonic anhydride to obtain
3)
Reaction with ethyl mercaptopropionate to give
4)
Is subjected to base catalytic ring closure to obtain
5. The production method according to claim 4, wherein, in the step 1),
and
the feeding molar ratio of (A) to (B) is 0.9-1.5: 1.0;
and/or, in the step 2),
the feeding molar ratio of the water to the trifluoromethanesulfonic anhydride is 0.1-0.3: 0.1 to 0.5;
and/or, in the step 3),
the feeding molar ratio of the compound to the ethyl mercaptopropionate is 0.1-0.3: 0.1 to 0.3;
and/or, in the step 4),
with alkali chargeThe molar ratio is 0.1-1.0: 1.0.
6. a method for producing the liquid crystal compound according to any one of claims 1 to 3, comprising the steps of:
1) to be provided with
And
as a raw material, through a Suzuki reaction to obtain
2)
Reacting with trifluoromethanesulfonic anhydride to obtain
3)
Reaction with ethyl mercaptopropionate to give
4)
Is subjected to base catalytic ring closure to obtain
7. The production method according to claim 6, wherein in the step 1),
and
the feeding molar ratio of (A) to (B) is 0.9-1.5: 1.0;
and/or, in the step 2),
the feeding molar ratio of the water to the trifluoromethanesulfonic anhydride is 0.1-0.3: 0.1 to 0.5;
and/or, in the step 3),
the feeding molar ratio of the compound to the ethyl mercaptopropionate is 0.1-0.3: 0.1 to 0.3;
and/or, in the step 4),
the feeding molar ratio of the alkali to the alkali is 0.1-1.0: 1.0.
8. a liquid crystal composition comprising the liquid crystal compound according to any one of claims 1 to 3.
9. The liquid crystal composition according to claim 8, wherein the liquid crystal compound is present in the liquid crystal composition in an amount of 1 to 60% by mass; preferably 3-50%; more preferably 5 to 25%.
10. Use of the liquid crystal compound according to any one of claims 1 to 3 and/or the liquid crystal composition according to claim 8 or 9 in the field of liquid crystal display;
preferably in liquid crystal display devices including TN, ADS, VA, PSVA, FFS or IPS liquid crystal displays.
Priority Applications (3)
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| CN202010626287.4A CN113881443A (en) | 2020-07-01 | 2020-07-01 | Liquid crystal compound containing dibenzothiophene structure and application thereof |
| PCT/CN2020/133014 WO2022000982A1 (en) | 2020-07-01 | 2020-12-01 | Liquid crystal compound containing dibenzothiophene structure and use thereof |
| TW109145807A TW202202488A (en) | 2020-07-01 | 2020-12-23 | Liquid crystal compound containing dibenzothiophene structure and use thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022218217A1 (en) * | 2021-04-15 | 2022-10-20 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display device thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109423296A (en) * | 2017-08-24 | 2019-03-05 | 北京八亿时空液晶科技股份有限公司 | A kind of dibenzothiophenes class negative dielectric anisotropic compound and its preparation method and application |
| TW201925435A (en) * | 2017-11-30 | 2019-07-01 | 日商捷恩智股份有限公司 | Compounds having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element |
| JP2019147859A (en) * | 2018-02-26 | 2019-09-05 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
| WO2020089140A1 (en) * | 2018-10-31 | 2020-05-07 | Merck Patent Gmbh | Dibenzofuran and dibenzothiophene derivatives |
| CN111170827A (en) * | 2018-11-13 | 2020-05-19 | Dic株式会社 | Compound, composition and liquid crystal display element |
| WO2020127172A1 (en) * | 2018-12-19 | 2020-06-25 | Merck Patent Gmbh | Liquid-crystalline medium and liquid-crystal display comprising the same and compounds |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2937342B1 (en) * | 2014-04-22 | 2016-11-30 | Merck Patent GmbH | 4,6-difluoro dibenzothiophene derivates |
| CN108264498B (en) * | 2017-08-16 | 2021-02-26 | 石家庄诚志永华显示材料有限公司 | Compound, liquid crystal medium containing compound and application of liquid crystal medium |
| CN111732569A (en) * | 2019-03-25 | 2020-10-02 | 捷恩智株式会社 | Liquid crystalline compound having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element |
-
2020
- 2020-07-01 CN CN202010626287.4A patent/CN113881443A/en active Pending
- 2020-12-01 WO PCT/CN2020/133014 patent/WO2022000982A1/en active Application Filing
- 2020-12-23 TW TW109145807A patent/TW202202488A/en unknown
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109423296A (en) * | 2017-08-24 | 2019-03-05 | 北京八亿时空液晶科技股份有限公司 | A kind of dibenzothiophenes class negative dielectric anisotropic compound and its preparation method and application |
| TW201925435A (en) * | 2017-11-30 | 2019-07-01 | 日商捷恩智股份有限公司 | Compounds having dibenzothiophene ring, liquid crystal composition, and liquid crystal display element |
| JP2019147859A (en) * | 2018-02-26 | 2019-09-05 | Jnc株式会社 | Liquid crystal composition and liquid crystal display element |
| WO2020089140A1 (en) * | 2018-10-31 | 2020-05-07 | Merck Patent Gmbh | Dibenzofuran and dibenzothiophene derivatives |
| CN111170827A (en) * | 2018-11-13 | 2020-05-19 | Dic株式会社 | Compound, composition and liquid crystal display element |
| WO2020127172A1 (en) * | 2018-12-19 | 2020-06-25 | Merck Patent Gmbh | Liquid-crystalline medium and liquid-crystal display comprising the same and compounds |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022218217A1 (en) * | 2021-04-15 | 2022-10-20 | 江苏和成显示科技有限公司 | Liquid crystal composition and liquid crystal display device thereof |
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| TW202202488A (en) | 2022-01-16 |
| WO2022000982A1 (en) | 2022-01-06 |
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