CN114517097B - Liquid crystal compound containing cyclohexene structure, and preparation method and application thereof - Google Patents
Liquid crystal compound containing cyclohexene structure, and preparation method and application thereof Download PDFInfo
- Publication number
- CN114517097B CN114517097B CN202011308752.6A CN202011308752A CN114517097B CN 114517097 B CN114517097 B CN 114517097B CN 202011308752 A CN202011308752 A CN 202011308752A CN 114517097 B CN114517097 B CN 114517097B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- crystal compound
- crystal composition
- compound containing
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 66
- 150000001875 compounds Chemical class 0.000 title claims abstract description 44
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 13
- 125000003545 alkoxy group Chemical group 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 4
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 4
- 229910052744 lithium Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- TVEXGJYMHHTVKP-UHFFFAOYSA-N 6-oxabicyclo[3.2.1]oct-3-en-7-one Chemical compound C1C2C(=O)OC1C=CC2 TVEXGJYMHHTVKP-UHFFFAOYSA-N 0.000 claims description 3
- 238000006297 dehydration reaction Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 230000018044 dehydration Effects 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
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000007787 solid Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000008346 aqueous phase Substances 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- AVOGLGBKOFOSBN-UHFFFAOYSA-N 1-ethoxy-2,3-difluorobenzene Chemical compound CCOC1=CC=CC(F)=C1F AVOGLGBKOFOSBN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical group [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Chemical group 0.000 description 1
- 229910052801 chlorine Chemical group 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- -1 propyltetrahydropyran cyclohexanone Chemical compound 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- 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
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D309/06—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
-
- 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
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
- C09K19/30—Non-steroidal liquid crystal compounds containing at least two non-condensed rings containing saturated or unsaturated non-aromatic rings, e.g. cyclohexane rings
-
- 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
-
- 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
- C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
- C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
Abstract
The invention belongs to the technical field of liquid crystal compounds, and particularly relates to a liquid crystal compound containing a cyclohexene structure, and a preparation method and application thereof. The liquid crystal compound containing cyclohexene structure has a structure shown in a general formula (I). The liquid crystal compound has higher clear point, higher optical anisotropy, low rotational viscosity, good thermal stability, chemical stability, optical stability, mechanical property and other properties, can improve the response speed of a liquid crystal display device, and has the characteristics of better charge retention rate and the like.
Description
Technical Field
The invention belongs to the technical field of liquid crystal compounds, and particularly relates to a liquid crystal compound containing a cyclohexene structure, and a preparation method and application thereof.
Background
Commercially available liquid crystal materials have been discovered since 30 years ago. The application of the liquid crystal material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. Liquid crystal materials have many advantages as novel display materials, such as extremely low power consumption and low driving voltage. Meanwhile, compared with other materials, the display device has the advantages of small volume, light weight, long service life, large information display quantity, no electromagnetic radiation and the like, and can be almost suitable for the requirements of various information displays, especially for TFT-LCD (thin film transistor technology) products.
In the TFT active matrix system, there are mainly main display modes such as a TN (Twisted Nematic) mode, an IPS (In-Plane Switching) mode, an FFS (Fringe Field Switching ) mode, and a VA (Vertical Alignment) mode.
At present, the technology of TFT-LCD products is mature gradually, the technical problems of visual angle, resolution, color saturation, brightness and the like are solved successfully, and large-size and medium-small-size TFT-LCD displays gradually occupy the mainstream position of flat panel displays in the respective fields. However, for dynamic display applications such as mobile phones and televisions, in order to achieve high-quality display, it is required that the liquid crystal material has a fast response speed and thus has a rotational viscosity γ1 as low as possible in order to eliminate display image sticking and tailing.
In order to improve the performance of the material and adapt to new requirements, the research on the synthesis and structure-performance relationship of novel structure liquid crystal compounds becomes an important work in the field of liquid crystals.
Disclosure of Invention
The first object of the present invention is to provide a novel liquid crystal compound containing cyclohexene structure, so as to improve the defects of the existing liquid crystal material and improve the application value of the liquid crystal compound.
The liquid crystal compound disclosed by the invention has a structure shown in a general formula (I):
in the general formula (I), R 1 And R is 2 The same or a different one of the above, each independently selected from the group consisting of-H, -Cl-F, -CN, -OCN, -OCF 3 、-CF 3 、-CHF 2 、-CH 2 F、-OCHF 2 、-SCN、-NCS、-SF 5 、C 1 -C 12 Alkyl or C of (2) 1-12 Wherein said C is an alkoxy group 1 -C 12 Alkyl or C of (2) 1-12 One or more hydrogens in the alkoxy group of (a) may be anyOptionally substituted by fluorine or chlorine, and one or more-CH 2 Optionally substituted with cyclopentyl, cyclopropyl or cyclobutyl;
A 1 selected from a single bond or one of the following groups:
preferably, in formula (I), R 1 And R is 2 Identical or different, each independently selected from-H, C 1 -C 7 Alkyl or C of (2) 1 -C 7 Wherein said C is an alkoxy group 1 -C 7 Alkyl or C of (2) 1 -C 7 One or more of the alkoxy groups-CH 2 Optionally substituted with cyclopentyl, cyclopropyl or cyclobutyl.
Further preferably, in the general formula (I), R 1 Selected from C 1 -C 7 Alkyl or C of (2) 1 -C 7 Alkoxy groups of (a); r is R 2 Selected from C 1 -C 7 Alkoxy groups of (a);
wherein said C 1 -C 7 Alkyl or C of (2) 1 -C 7 One or more of the alkoxy groups-CH 2 Optionally substituted with cyclopentyl, cyclopropyl or cyclobutyl.
Preferably, in formula (I), the A 1 One selected from the following groups:
preferably, the liquid crystal compound is selected from one or more of the following compounds:
/>
/>
/>
/>
/>
/>
/>
/>
。
a second object of the present invention is to provide a method for preparing the above liquid crystal compound, which comprises the following synthetic routes:
the method specifically comprises the following steps:
1)preparation of lithium reagent with butyllithium, lithium reagent and +.>Reacting to obtain
2)Reacting with p-toluenesulfonic acid for dehydration to obtain
Wherein R is 1 、R 2 、A 1 Is as defined above.
The method according to the invention may, if necessary, involve conventional post-treatments, such as in particular: extracting with dichloromethane, ethyl acetate or toluene, separating, 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 adopting the preparation method.
A third object of the present invention is to protect a composition containing said liquid crystal compound. Among them, the amount of the liquid crystal compound added is preferably 1 to 60%, more preferably 3 to 50%, still more preferably 5 to 25%. It is expected by those skilled in the art that the addition of the above liquid crystal compound can further improve the optical anisotropy of the conventional liquid crystal composition and has the technical effect of shortening the response time.
A fourth object of the present invention is to protect the application of the above liquid crystal compound and the composition containing the above liquid crystal compound in the field of liquid crystal display, preferably in a liquid crystal display device, which is further preferably a VA or PSVA display. The liquid crystal composition has the advantage of shortening response time after being applied to a liquid crystal display device.
The invention has the following beneficial effects:
the liquid crystal compound has higher clear point, higher optical anisotropy, low rotational viscosity, good heat stability, chemical stability, optical stability, mechanical property and other properties, improves the response speed of a liquid crystal display device, and has the characteristics of better charge retention rate and the like.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The raw materials are commercially available from public sources (e.g., beijing eight hundred million space time supplies) unless otherwise specified.
Example 1
The present embodiment relates to a liquid crystal compound having the following structural formula:
the synthetic route is as follows:
the specific synthesis steps are as follows:
1. synthesis of BYLC-01
Into a 1L four-necked flask, 0.2L of anhydrous tetrahydrofuran and 31.6g (0.2 mol) of 2, 3-difluorophenetole (BYLC-01-1) were charged and purged 3 times with nitrogen. Cooling to-70 ℃. 2.5M 80ml of butyllithium is added dropwise, the dropping speed is controlled, and the temperature is controlled between-70 ℃ and-80 ℃. After the dripping is finished, the heat preservation is continued for 1h.
A mixed solution of 44.8g of propyltetrahydropyran cyclohexanone (BYLC-01-2) and 150L of tetrahydrofuran was added dropwise thereto, and the reaction temperature was kept at-70 to-80 ℃. After the dripping is finished, the temperature is kept for 3 hours, sampling and tracking are carried out, and when the residual raw materials are less than 0.5%, the reaction is stopped.
200mL of toluene is added into the reaction solution, tetrahydrofuran is distilled under normal pressure at 80-90 ℃, most tetrahydrofuran is distilled, the reaction solution is cooled to room temperature (20-30 ℃), 0.2L of hydrochloric acid and 0.5L of ice water are slowly poured into the reaction solution for hydrolysis, the external part is cooled by a refrigerating fluid, and the temperature is controlled at 15-25 ℃. Stirring, standing and separating after pouring. The aqueous phase was extracted twice with 1l x 2 toluene and the organic layers were combined and washed twice with 1l x 2 saturated brine to neutrality.
The organic phase was concentrated (normal pressure) and warmed to 110 ℃, and the obtained concentrate, GC main product purity 88%, was used directly for the next dehydration reaction.
To a 51L four-necked flask, the concentrated solution, 10g of p-toluenesulfonic acid, 1.5g of BHT and 100mL of ethylene glycol were added, the temperature was raised to 110℃and the reaction mixture was refluxed and water was separated by a water separator. The reflux rate was controlled and after 3 hours sampling was started, about 50g of water was separated. Heating was stopped, and stirring was stopped until the temperature was lowered to room temperature.
Adding 1L of pure water into the reaction solution under stirring, standing, separating a lower aqueous phase, adding 0.2L of pure water into an upper organic phase, stirring, standing, separating, mixing the aqueous phases, extracting once with 100mL of toluene, combining the organic phases obtained by the two steps, washing with 0.2L of 3 saturated brine for 3 times, and discarding the aqueous phase. The resulting organic phase was added to 50g of anhydrous sodium sulfate and dried for 2 hours, filtered, and the filter cake was rinsed with 100mL of toluene.
The filtrate is pressed into a silica gel column formed by 100g of silica gel, normal pressure column passing is started, and light yellow column passing liquid is decompressed and concentrated after column passing.
The obtained column liquid is heated to 60.0-70.0 ℃, vacuum degree is minus 0.08-minus 0.09MPa, concentrated, and recrystallized twice by absolute ethyl alcohol to obtain 54.6g of white solid BYLC-01. Purity 99.9% and yield 75%.
The resulting white solid BYLC-01 was analyzed by GC-MS and the product had an M/z of 3364.2 (M+).
Example 2
The present embodiment relates to a liquid crystal compound having the following structural formula:
the synthetic route was compared with example 1 with only a simple replacement of the starting materials;
the resulting white solid BYLC-02 was analyzed by GC-MS and the product had an M/z of 366.2 (M+).
Example 3
The present embodiment relates to a liquid crystal compound having the following structural formula:
the resulting white solid BYLC-03 was analyzed by GC-MS and the M/z of the product was 364.2 (M+).
Example 4
The present embodiment relates to a liquid crystal compound having the following structural formula:
the synthetic route was compared to example 3 with only a simple replacement of the starting materials;
the resulting white solid BYLC-04 was analyzed by GC-MS and the product had an M/z of 366.2 (M+).
Example 5
The present embodiment relates to a liquid crystal compound having the following structural formula:
the synthetic route was compared to example 3 with only a simple replacement of the starting materials;
the resulting white solid BYLC-05 was analyzed by GC-MS and the M/z of the product was 392.2 (M+).
Example 6
The present embodiment relates to a liquid crystal compound having the following structural formula:
the resulting white solid BYLC-06 was analyzed by GC-MS and the product had an M/z of 418.2 (M+).
Experimental example
This experimental example relates to the measurement of the relevant properties of the compounds described in examples 1 to 6.
According to conventional detection methods in the art, such as gamma 1 detection using a viscometer, delta n detection using an Abbe refractometer, cp detection using a differential thermal scanner.
Obtaining various performance parameters of the liquid crystal compound through linear fitting, wherein the specific meaning of each performance parameter is as follows:
Δn represents optical anisotropy (25 ℃); γ1 represents the rotational viscosity (mPas, 25 ℃); cp represents a clearing point.
The liquid crystal compounds prepared in examples 1 to 6 and the liquid crystal compounds of comparative examples 1 to 3 were subjected to comparative arrangement of performance parameter data, and the detection results are shown in Table 1:
table 1: results of performance test of liquid Crystal Compound
As is apparent from the test results of Table 1, the liquid crystal compound provided by the present invention has a lower rotational viscosity γ1, a larger optical anisotropy Deltan, and a higher clearing point Cp than the conventional compound having a similar chemical structure, and can improve the response time and increase the working temperature of the liquid crystal composition.
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 containing cyclohexene structure is characterized by having a structure shown in a general formula (I):
in the general formula (I), R 1 Selected from C 1 -C 7 Alkyl or C of (2) 1 -C 7 Alkoxy groups of (a); r is R 2 Selected from C 1 -C 7 Alkoxy groups of (a);
wherein said C 1 -C 7 Alkyl or C of (2) 1 -C 7 One or more of the alkoxy groups-CH 2 Optionally substituted with cyclopentyl, cyclopropyl or cyclobutyl;
A 1 selected from the group consisting ofOne or two of:
2. the cyclohexene structure-containing liquid crystal compound according to claim 1, wherein the liquid crystal compound represented by the general formula (I) is selected from one or more of the following structures:
/>
。
3. a process for preparing a liquid crystalline compound according to claim 1 or 2, characterized by the following synthetic route:
the method specifically comprises the following steps:
1)preparation of lithium reagent with butyllithium, lithium reagent and +.>Reacting to obtain
2)Reacting with p-toluenesulfonic acid for dehydration to obtain
Wherein R is 1 、R 2 、A 1 Is as defined in claim 1.
4. A liquid crystal composition comprising the liquid crystal compound according to claim 1 or 2.
5. A liquid crystal composition according to claim 3, wherein the mass percentage of the liquid crystal compound in the liquid crystal composition is 1 to 60%.
6. The liquid crystal composition according to claim 5, wherein the mass percentage of the liquid crystal compound in the liquid crystal composition is 3 to 50%.
7. The liquid crystal composition according to claim 6, wherein the mass percentage of the liquid crystal compound in the liquid crystal composition is 5 to 25%.
8. Use of a liquid crystal compound according to claim 1 or 2 or a liquid crystal composition according to any one of claims 4 to 7 in the field of liquid crystal display.
9. The use according to claim 8, wherein the liquid crystal display field is a liquid crystal display device.
10. The use according to claim 9, wherein the liquid crystal display device is a VA or PSVA display.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011308752.6A CN114517097B (en) | 2020-11-20 | 2020-11-20 | Liquid crystal compound containing cyclohexene structure, and preparation method and application thereof |
| TW110142625A TWI820516B (en) | 2020-11-20 | 2021-11-16 | A kind of liquid crystal composition containing cyclohexene structure and its preparation method and application |
| PCT/CN2021/131188 WO2022105790A1 (en) | 2020-11-20 | 2021-11-17 | Liquid crystal compound containing cyclohexene structure, preparation method therefor and use thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011308752.6A CN114517097B (en) | 2020-11-20 | 2020-11-20 | Liquid crystal compound containing cyclohexene structure, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114517097A CN114517097A (en) | 2022-05-20 |
| CN114517097B true CN114517097B (en) | 2024-01-09 |
Family
ID=81595049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011308752.6A Active CN114517097B (en) | 2020-11-20 | 2020-11-20 | Liquid crystal compound containing cyclohexene structure, and preparation method and application thereof |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN114517097B (en) |
| TW (1) | TWI820516B (en) |
| WO (1) | WO2022105790A1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115612503A (en) * | 2022-08-29 | 2023-01-17 | 重庆汉朗精工科技有限公司 | Fast response negative liquid crystal composition and liquid crystal display |
| CN116286024A (en) * | 2022-09-08 | 2023-06-23 | 重庆汉朗精工科技有限公司 | Negative liquid crystal composition and application thereof |
| CN116286023A (en) * | 2022-09-08 | 2023-06-23 | 重庆汉朗精工科技有限公司 | Negative liquid crystal composition and application thereof in liquid crystal display device |
| CN115806466A (en) * | 2022-12-28 | 2023-03-17 | 北京燕化集联光电技术有限公司 | Negative liquid crystal compound and application thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724407A (en) * | 2008-10-30 | 2010-06-09 | 默克专利股份有限公司 | Liquid-crystalline medium and liquid crystal display |
| CN104591983A (en) * | 2015-02-15 | 2015-05-06 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound and liquid crystal medium containing liquid crystal compound |
| CN105295952A (en) * | 2014-06-18 | 2016-02-03 | 捷恩智株式会社 | Liquid crystal compound and use thereof, liquid crystal composition and liquid crystal display element |
| CN107151557A (en) * | 2016-03-03 | 2017-09-12 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing cyclohexene compound and application |
| CN107760317A (en) * | 2016-08-22 | 2018-03-06 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing cyclohexenyl group liquid-crystal compounds and its application |
| CN110819360A (en) * | 2018-08-10 | 2020-02-21 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition of cyclopentyl-containing cyclohexene-group negative monomer and liquid crystal display element thereof |
| CN111826169A (en) * | 2019-04-22 | 2020-10-27 | 捷恩智株式会社 | Liquid crystal composition, use thereof, and liquid crystal display element |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1897928B1 (en) * | 2006-09-06 | 2010-10-27 | Chisso Corporation | Chlorofluorobenzene liquid crystal compound, liquid crystal composition and liquid crystal display device |
| ATE517968T1 (en) * | 2006-09-06 | 2011-08-15 | Jnc Corp | CYCLOHEXENE DERIVATIVES WITH ALKENYL, LIQUID CRYSTAL COMPOSITION AND LIQUID CRYSTAL DISPLAY DEVICE |
| CN104003964B (en) * | 2014-06-06 | 2016-09-07 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal compounds containing amylene oxide ring and application thereof |
| US11326102B2 (en) * | 2017-09-08 | 2022-05-10 | Merck Patent Gmbh | Liquid-crystalline medium and liquid-crystal display comprising the same |
| JP2020140191A (en) * | 2019-02-22 | 2020-09-03 | Jnc株式会社 | Liquid crystal composition and optical switching element |
-
2020
- 2020-11-20 CN CN202011308752.6A patent/CN114517097B/en active Active
-
2021
- 2021-11-16 TW TW110142625A patent/TWI820516B/en active
- 2021-11-17 WO PCT/CN2021/131188 patent/WO2022105790A1/en active Application Filing
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101724407A (en) * | 2008-10-30 | 2010-06-09 | 默克专利股份有限公司 | Liquid-crystalline medium and liquid crystal display |
| CN105295952A (en) * | 2014-06-18 | 2016-02-03 | 捷恩智株式会社 | Liquid crystal compound and use thereof, liquid crystal composition and liquid crystal display element |
| CN104591983A (en) * | 2015-02-15 | 2015-05-06 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound and liquid crystal medium containing liquid crystal compound |
| CN107151557A (en) * | 2016-03-03 | 2017-09-12 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing cyclohexene compound and application |
| CN107760317A (en) * | 2016-08-22 | 2018-03-06 | 北京八亿时空液晶科技股份有限公司 | A kind of liquid-crystal composition containing cyclohexenyl group liquid-crystal compounds and its application |
| CN110819360A (en) * | 2018-08-10 | 2020-02-21 | 石家庄诚志永华显示材料有限公司 | Liquid crystal composition of cyclopentyl-containing cyclohexene-group negative monomer and liquid crystal display element thereof |
| CN111826169A (en) * | 2019-04-22 | 2020-10-27 | 捷恩智株式会社 | Liquid crystal composition, use thereof, and liquid crystal display element |
Also Published As
| Publication number | Publication date |
|---|---|
| TW202220966A (en) | 2022-06-01 |
| TWI820516B (en) | 2023-11-01 |
| CN114517097A (en) | 2022-05-20 |
| WO2022105790A1 (en) | 2022-05-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN114517097B (en) | Liquid crystal compound containing cyclohexene structure, and preparation method and application thereof | |
| KR101431935B1 (en) | Cyclohexane compound and liquid crystal composition containing said compound | |
| CN109206400B (en) | Liquid crystal compound containing dibenzothiophene structure and application thereof | |
| JP4876420B2 (en) | Difluorobenzene derivative | |
| CN109423296B (en) | Dibenzothiophene negative dielectric anisotropy compound and preparation method and application thereof | |
| CN109207160B (en) | Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof | |
| CN103058886B (en) | Poly-fluorine poly-cyanogen liquid crystal compound as well as preparation method and application thereof | |
| CN108728112A (en) | A kind of liquid-crystal compounds of negative dielectric anisotropic and the preparation method and application thereof | |
| CN103242854B (en) | Fluorine-containing liquid crystal compound | |
| CN112980461A (en) | Negative dielectric liquid crystal compound and preparation and application thereof | |
| CN109082281B (en) | Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof | |
| CN108690636B (en) | Liquid crystal compound with negative dielectric anisotropy as well as preparation method and application thereof | |
| CN107400517B (en) | Cyclopentyl negative dielectric anisotropy liquid crystal compound, composition and application | |
| CN114105941B (en) | Novel liquid crystal compound and preparation method and application thereof | |
| CN107286953B (en) | Cyclopentyl negative dielectric anisotropy liquid crystal compound and composition and application thereof | |
| CN114105966A (en) | Liquid crystal compound and preparation method and application thereof | |
| CN113881443A (en) | Liquid crystal compound containing dibenzothiophene structure and application thereof | |
| CN113004904B (en) | Liquid crystal compound containing cyclohexene structure and preparation method thereof | |
| CN107286950A (en) | A kind of cyclopenta liquid-crystal compounds, composition and its application | |
| CN109423298B (en) | Novel dibenzothiophene liquid crystal compound and preparation method and application thereof | |
| CN113265260B (en) | Liquid crystal compound containing cyclohexene structure and preparation method and application thereof | |
| CN107286949B (en) | A kind of liquid-crystal compounds of cyclopenta class negative dielectric anisotropic and its application | |
| CN112980460A (en) | Liquid crystal compound and preparation method and application thereof | |
| CN113493689B (en) | Liquid crystal compound containing difluoromethoxy bridge bond and preparation method and application thereof | |
| CN112980459A (en) | Liquid crystal compound containing dibenzothiophene structure and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |