CN118146805A - Diphenyl thiophene liquid crystal compound and its preparation method and application - Google Patents
Diphenyl thiophene liquid crystal compound and its preparation method and application Download PDFInfo
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- CN118146805A CN118146805A CN202211559665.7A CN202211559665A CN118146805A CN 118146805 A CN118146805 A CN 118146805A CN 202211559665 A CN202211559665 A CN 202211559665A CN 118146805 A CN118146805 A CN 118146805A
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 75
- 150000001875 compounds Chemical class 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title abstract description 11
- RZFOAVRHEGQZRV-UHFFFAOYSA-N 2,3-diphenylthiophene Chemical compound S1C=CC(C=2C=CC=CC=2)=C1C1=CC=CC=C1 RZFOAVRHEGQZRV-UHFFFAOYSA-N 0.000 title abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 84
- 125000003545 alkoxy group Chemical group 0.000 claims description 36
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 16
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 16
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 16
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 7
- 125000003342 alkenyl group Chemical group 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- LXXNWCFBZHKFPT-UHFFFAOYSA-N Ethyl 2-mercaptopropionate Chemical compound CCOC(=O)C(C)S LXXNWCFBZHKFPT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000004327 boric acid Substances 0.000 claims description 4
- -1 boric acid ester Chemical class 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 238000001465 metallisation Methods 0.000 claims description 2
- 125000001979 organolithium group Chemical group 0.000 claims description 2
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000000463 material Substances 0.000 abstract description 11
- 230000003287 optical effect Effects 0.000 abstract description 7
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 230000003245 working effect Effects 0.000 abstract description 2
- 239000003989 dielectric material Substances 0.000 abstract 1
- 239000007787 solid Substances 0.000 description 19
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 15
- 238000004458 analytical method Methods 0.000 description 11
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 238000001953 recrystallisation Methods 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 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
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 238000013375 chromatographic separation Methods 0.000 description 1
- 238000011097 chromatography purification 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
- 239000012769 display material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001704 evaporation Methods 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
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- USFPINLPPFWTJW-UHFFFAOYSA-N tetraphenylphosphonium Chemical compound C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 USFPINLPPFWTJW-UHFFFAOYSA-N 0.000 description 1
- 238000004809 thin layer chromatography Methods 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 1
- LHJSLDBKUGXPMI-UHFFFAOYSA-N tris(2-methylpropyl) borate Chemical compound CC(C)COB(OCC(C)C)OCC(C)C LHJSLDBKUGXPMI-UHFFFAOYSA-N 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005406 washing Methods 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 materials, in particular to a diphenyl thiophene liquid crystal compound and a preparation method and application thereof. The invention provides a diphenyl thiophene liquid crystal compound, a preparation method and application thereof, and the diphenyl thiophene liquid crystal compound has a structural formula as shown in a general formula (I):
Description
Technical Field
The invention relates to the technical field of liquid crystal materials, in particular to a diphenyl thiophene liquid crystal compound and a preparation method and application thereof.
Background
In recent years, liquid crystal display devices have been developed more and more rapidly, and various types such as a vehicle-mounted small-sized liquid crystal display device, a portable liquid crystal display device, an ultra-thin liquid crystal display device, and the like have also been developed. Development in the field is progressing, taking a television as an example, and the television is characterized by light weight, small occupied space, convenient movement, notebook personal computers, mobile phones and the like.
The liquid crystal material has great research value and good application prospect as an environment material in the fields of information display materials, organic optoelectronic materials and the like. 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 large-size and medium-small-size TFT-LCD displays gradually occupy the mainstream position of flat panel displays in the respective fields. However, the requirements for display technology are continuously increasing, and the liquid crystal display is required to realize faster response, lower driving voltage to reduce power consumption, and the like, and the liquid crystal material is also required to have low-voltage driving, fast response, wide temperature range and good low-temperature stability.
The liquid crystal material plays an important role in improving the performance of a liquid crystal display, and in order to improve the performance of the material and enable the material to adapt to new requirements, the research on the synthesis and structure-performance relationship of a novel structure liquid crystal compound becomes an important work in the field of liquid crystals.
Disclosure of Invention
The invention provides a diphenyl thiophene liquid crystal compound and a preparation method and application thereof, which are used for solving the defect of poor performance of a liquid crystal material in the prior art and realizing a liquid crystal material with low-voltage driving, quick response, wide temperature range and good low-temperature stability.
The invention provides a liquid crystal compound, which has a structural formula shown in a general formula (I):
in the general formula I, R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with F, an alkoxy group having 1 to 10 carbon atoms substituted with F, a cyclopropyl group, a cyclobutyl group or a cyclopentyl group;
R 2 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with F, an alkoxy group having 1 to 10 carbon atoms substituted with F, an alkenyloxy group having 2 to 10 carbon atoms substituted with F, an alkoxy group having 1 to 10 carbon atoms substituted with cyclopropyl, cyclobutyl or cyclopentyl;
z 1 represents a single bond, -O-, -CH 2-、-CH2CH2 -, or-CH 2 O-;
Z 2 represents-CH 2-、-CH2CH2-、-CH2 O-or-CF 2 O-.
Preferably, R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with F, an alkoxy group having 1 to 6 carbon atoms substituted with F, a cyclopropyl group, a cyclobutyl group or a cyclopentyl group;
R 2 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with F, an alkoxy group having 1 to 5 carbon atoms substituted with F, an alkenyloxy group having 2 to 5 carbon atoms substituted with F, an alkoxy group having 1 to 5 carbon atoms substituted with cyclopropyl, cyclobutyl or cyclopentyl;
z 1 represents a single bond, -O-, -CH 2-、-CH2CH2 -, or-CH 2 O-;
Z 2 represents a single bond, -O-, -CH 2-、-CH2CH2 -, or-CH 2 O-.
Preferably, R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with F, an alkoxy group having 1 to 6 carbon atoms substituted with F, a cyclopropyl group, a cyclobutyl group or a cyclopentyl group;
R 2 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with F, an alkoxy group having 1 to 5 carbon atoms substituted with F, an alkenyloxy group having 2 to 5 carbon atoms substituted with F, an alkoxy group having 1 to 5 carbon atoms substituted with cyclopropyl, cyclobutyl or cyclopentyl;
z 1 represents a single bond;
Z 2 represents-CH 2 O-.
Preferably, R 1 represents an alkyl group having 1 to 6 carbon atoms, cyclopropyl, cyclobutyl or cyclopentyl;
R 2 represents an alkoxy group of 1 to 5 carbon atoms, an alkenyloxy group of 2 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms substituted with F, an alkenyloxy group of 2 to 5 carbon atoms substituted with F, an alkoxy group of 1 to 5 carbon atoms substituted with cyclopropyl, cyclobutyl or cyclopentyl;
z 1 represents a single bond;
Z 2 represents-CH 2 O-.
Preferably, the liquid crystal compound has any one of the following structural formulas:
the invention further provides a preparation method of the liquid crystal compound, and the synthetic route comprises the following steps:
Preferably, the preparation method comprises the following steps:
1) Will be Carrying out metallization reaction with an organolithium reagent and then carrying out reaction with boric acid ester to obtain
2)And/>Through the suzuki reaction, obtain
3)Substitution reaction with (CF 3SO2)2 O)
4)With ethyl mercaptopropionate to obtain
5)The ring closure is carried out under the catalysis of alkali to obtainWherein R 1、Z1、Z2、R2 is the same as the preceding reference.
Preferably, in step 1) of the above method,The molar ratio of the organic lithium reagent to the organic lithium reagent is 1:1.0 to 2.0, and the feeding mole ratio of the boric acid ester is 1:1.0 to 3.0.
More preferably, the reaction temperature is-100 to-50 ℃.
Wherein,Obtained by public commercial means; the organic lithium reagent is selected from one or more of sec-butyllithium, tert-butyllithium or n-butyllithium; the boric acid ester is selected from one or more of trimethyl borate, triisopropyl borate, tributyl borate and triisobutyl borate.
Preferably, in step 2) of the above method,And/>The feeding mole ratio of (2) is 1.0:1.0 to 1.5.
More preferably, the reaction temperature is 60 to 140 ℃.
Wherein the raw materials areAre commercially available through public pathways.
Preferably, in step 3) of the above method,The molar ratio of the catalyst to the (CF 3SO2)2 O) is 1.0-2.0:2.
More preferably, the reaction temperature is 0 to 20 ℃.
Preferably, in the step 4),The feeding molar ratio of the catalyst to the ethyl mercaptopropionate is 1:1.0 to 2.0.
More preferably, the reaction temperature is 50 to 150 ℃.
Preferably, in the step 5)The feeding mole ratio of the alkali to the alkali is 1:1.0-4.0.
More preferably, the reaction temperature is 80 to 150 ℃.
The liquid crystal compound can be obtained more stably and efficiently by adopting the preparation method.
In the present invention, a person skilled in the art can use a conventional post-treatment method according to actual needs when using the above-mentioned preparation method. Preferably, the conventional post-treatment includes: 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 invention also provides a liquid crystal composition, which contains the liquid crystal compound.
Preferably, the mass percentage of the liquid crystal compound in the liquid crystal composition is 0.01-60%;
More preferably 0.1 to 50%; more preferably 0.1 to 40%.
The invention further provides application of the liquid crystal compound or the liquid crystal composition in the field of liquid crystal display, preferably application in a liquid crystal display device.
More preferably, the liquid crystal display device includes VA, TN, STN, FFS or IPS liquid crystal display.
According to the diphenyl thiophene liquid crystal compound, the preparation method and the application thereof, the structure is optimized, so that the liquid crystal compound has relatively large dielectric anisotropy, high clearing point, relatively high optical anisotropy, moderate rotational viscosity and liquid crystal intersolubility, excellent low-temperature working effect, good thermal stability, chemical stability, optical stability, mechanical property and the like; thereby effectively reducing the driving voltage, improving the response speed of the liquid crystal display device, and simultaneously having the characteristics of moderate optical anisotropy value, high charge retention rate and the like.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The starting materials are available from published commercial sources unless otherwise specified.
Example 1
The structural formula of the liquid crystal compound is as follows:
the specific synthetic route is as follows:
the method comprises the following specific steps:
(1) Synthesis of Compound BYLC-01-1:
Under nitrogen, 69.4g (0.261 mol) were added to the flask 150Ml of tetrahydrofuran, dropwise adding 0.45mol of n-hexane solution of n-butyllithium at the temperature of-70 to-80 ℃, reacting for 1 hour at the temperature of-60 to-70 ℃ after dropwise adding 48.0g of trimethyl borate (0.45 mol), and naturally returning to the temperature of-30 ℃. 400ml of 2M aqueous hydrochloric acid was added for acidification, conventional work-up and recrystallization from petroleum ether gave 72.8g of a pale yellow solid (Compound BYLC-01-1,0.239 mol), HPLC:99.7%, yield: 90%.
(2) Synthesis of Compound BYLC-01-2:
into a reaction flask, 72.8g of Compound BYLC-01-1 (0.235 mol), 61.5g of Compound were charged under nitrogen (0.235 Mol), 200ml of N, N-dimethylformamide, 100ml of deionized water, 72.8g of anhydrous potassium carbonate (0.53 mol), 0.5g of tetraphenylphosphine palladium, and heating to 70℃for reaction for 3 hours. Conventional work-up, purification by chromatography, elution with n-hexane, recrystallization from ethanol afforded 84.2g of a white solid (compound BYLC-01-2,0.188 mol), GC:99.8%, yield: 80%.
(3) Synthesis of Compound BYLC-01-3:
Into a 500ml three-necked flask, 83.5g of compound BYLC-01-2 (0.188 mol), 0.3g of succinic acid, 13.4g of Et3N and 180ml of DCM were added, stirring was started, the temperature was controlled at 5-10℃under N2 protection, 85g (CF 3SO2)2 O (0.300 mol) was added dropwise, after the addition, stirring was naturally carried out overnight, the reaction solution was washed twice with water (200 ml. Times.2), dried over anhydrous sodium sulfate, passed through a 40g silica gel column and spin-dried to give a white solid (compound BYLC-01-3, 0.67 mol) 97g, GC:99.8% yield: 89%.
(4) Synthesis of Compound BYLC-01-4
To the reaction flask, 97g of compound BYLC-01-4, (0.167 mol) 24.5g of ethyl mercaptopropionate, 25.6g of N, N-diisopropylethylamine, 0.7g of 2-dicyclohexylphosphine-2, 4, 6-triisopropylbiphenyl, 0.7g of tris (dibenzylideneacetone) dipalladium and 280ml of dioxane were charged under nitrogen atmosphere, and the reaction was carried out at a temperature of 100℃to 105℃for 6 hours. Conventional work-up, purification by chromatography, elution with n-hexane, afforded 70.6g of a pale yellow liquid (Compound BYLC-01-4), GC:95.8%, yield: 75%.
(5) Synthesis of Compound BYLC-01:
70g of compound BYLC-01-4,0.125mol, 200ml of N, N-dimethylformamide and 37g of potassium tert-butoxide are added into a reaction bottle under the protection of nitrogen, and the reaction is completed by TLC (thin layer chromatography) after the reaction is carried out for 3 hours at the temperature of 130-140 ℃. Conventional work-up, chromatographic purification, elution with n-hexane, and recrystallization from ethanol gave 35.5g of a white solid (compound BYLC-01,0.08 mol), GC:99.9%, yield 64%;
the resulting white solid BYLC-01 was analyzed by GC-MS and the product had an M/z of 444 (M+).
Example 2
The structural formula of the liquid crystal compound is as follows:
Analysis of the resulting white solid BYLC-02 by GC-MS gave a product with an M/z of 416 (M+).
Example 3
The structural formula of the liquid crystal compound is as follows:
/>
Analysis of the resulting white solid BYLC-03 by GC-MS gave a product with M/z 442 (M+).
Example 4
The structural formula of the liquid crystal compound is as follows:
Analysis of the resulting white solid BYLC-04 by GC-MS gave a M/z of 472 (M+).
Example 5
The structural formula of the liquid crystal compound is as follows:
analysis of the resulting white solid BYLC-05 by GC-MS gave a product M/z of 444 (M+).
Example 6
The structural formula of the liquid crystal compound is as follows:
Analysis of the resulting white solid BYLC-06 by GC-MS gave a product with an M/z of 470 (M+).
Example 7
The structural formula of the liquid crystal compound is as follows:
analysis of the resulting white solid BYLC-07 by GC-MS gave a product with an M/z of 470 (M+).
Example 8
The structural formula of the liquid crystal compound is as follows:
Analysis of the resulting white solid BYLC-08 by GC-MS gave a product with M/z of 442 (M+).
Example 9
The structural formula of the liquid crystal compound is as follows:
Analysis of the resulting white solid BYLC-09 by GC-MS gave a product with M/z of 468 (M+).
Example 10
The structural formula of the liquid crystal compound is as follows:
/>
The resulting white solid BYLC-12 was analyzed by GC-MS and the product had an M/z of 456 (M+).
Example 11
The structural formula of the liquid crystal compound is as follows:
the resulting white solid BYLC-13 was analyzed by GC-MS and the product had an M/z of 428 (M+).
Example 12
The structural formula of the liquid crystal compound is as follows:
Analysis of the resulting white solid BYLC-14 by GC-MS gave a product with M/z of 434 (M+).
Example 13
The structural formula of the liquid crystal compound is as follows:
the resulting white solid BYLC-15 was analyzed by GC-MS and the M/z of the product was 450 (M+).
Example 14
The structural formula of the liquid crystal compound is as follows:
Analysis of the resulting white solid BYLC-16 by GC-MS gave a product M/z of 478 (M+).
Example 15
The structural formula of the liquid crystal compound is as follows:
Analysis of the resulting white solid BYLC-17 by GC-MS gave a product with an M/z of 462 (M+).
Comparative example
CP-1
Experimental example
According to conventional detection methods in the art, such as gamma 1 detection using a viscometer, delta n detection using an Abbe refractometer, delta epsilon detection using INSTEC liquid crystal detection instruments.
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 ℃); delta epsilon represents dielectric anisotropy (25 ℃,1000 Hz); γ1 represents the rotational viscosity (mPas, 25 ℃).
The performance parameter data of the compounds prepared in the examples are compared and arranged, and the detection results are shown in table 1:
From the experimental data, the liquid crystal compound provided by the invention has larger negative dielectric anisotropy and lower rotational viscosity.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A liquid crystal compound, characterized by having a structural formula as described in general formula (I):
In the general formula (I), R 1 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with F, an alkoxy group having 1 to 10 carbon atoms substituted with F, a cyclopropyl group, a cyclobutyl group or a cyclopentyl group;
R 2 represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyloxy group having 2 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms substituted with F, an alkoxy group having 1 to 10 carbon atoms substituted with F, an alkenyloxy group having 2 to 10 carbon atoms substituted with F, an alkoxy group having 1 to 10 carbon atoms substituted with cyclopropyl, cyclobutyl or cyclopentyl;
z 1 represents a single bond, -O-, -CH 2-、-CH2CH2 -, or-CH 2 O-;
Z 2 represents-CH 2-、-CH2CH2-、-CH2 O-or-CF 2 O-.
2. The liquid crystal compound according to claim 1, wherein R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with F, an alkoxy group having 1 to 6 carbon atoms substituted with F, a cyclopropyl group, a cyclobutyl group, or a cyclopentyl group;
R 2 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with F, an alkoxy group having 1 to 5 carbon atoms substituted with F, an alkenyloxy group having 2 to 5 carbon atoms substituted with F, an alkoxy group having 1 to 5 carbon atoms substituted with cyclopropyl, cyclobutyl or cyclopentyl;
z 1 represents a single bond, -O-, -CH 2-、-CH2CH2 -, or-CH 2 O-;
Z 2 represents a single bond, -O-, -CH 2-、-CH2CH2 -, or-CH 2 O-.
3. A liquid crystal compound according to claim 1 or 2, wherein R 1 represents an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkyl group having 1 to 6 carbon atoms substituted with F, an alkoxy group having 1 to 6 carbon atoms substituted with F, a cyclopropyl group, a cyclobutyl group, or a cyclopentyl group;
R 2 represents an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkenyloxy group having 2 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms substituted with F, an alkoxy group having 1 to 5 carbon atoms substituted with F, an alkenyloxy group having 2 to 5 carbon atoms substituted with F, an alkoxy group having 1 to 5 carbon atoms substituted with cyclopropyl, cyclobutyl or cyclopentyl;
z 1 represents a single bond;
Z 2 represents-CH 2 O-.
4. A compound according to any one of claims 1 to 3, wherein R 1 represents an alkyl group having 1 to 6 carbon atoms, cyclopropyl, cyclobutyl or cyclopentyl;
R 2 represents an alkoxy group of 1 to 5 carbon atoms, an alkenyloxy group of 2 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms substituted with F, an alkenyloxy group of 2 to 5 carbon atoms substituted with F, an alkoxy group of 1 to 5 carbon atoms substituted with cyclopropyl, cyclobutyl or cyclopentyl;
z 1 represents a single bond;
Z 2 represents-CH 2 O-.
5. A compound according to any one of claims 1 to 4, having the formula:
6. the method for producing a liquid crystal compound according to any one of claims 1 to 5, wherein the synthetic route comprises:
7. the method for producing a liquid crystal compound according to claim 6, comprising the steps of:
1) Will be Carrying out metallization reaction with an organolithium reagent and then carrying out reaction with boric acid ester to obtain
2)And/>Through the suzuki reaction, obtain
3)Substitution reaction with (CF 3SO2)2 O)
4)With ethyl mercaptopropionate to obtain
5)The ring closure is carried out under the catalysis of alkali to obtainWherein R 1、Z1、Z2、R2 is as defined in any one of claims 1 to 5.
8. A liquid crystal composition comprising the liquid crystal compound according to any one of claims 1 to 5.
9. The liquid crystal composition according to claim 8, wherein the mass percentage of the liquid crystal compound in the liquid crystal composition is 0.01 to 60%; preferably 0.1 to 50%; more preferably 0.1 to 40%.
10. Use of a liquid crystal compound according to any one of claims 1 to 5 or a liquid crystal composition according to claim 8 or 9 in the field of liquid crystal display, preferably in a liquid crystal display device.
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| CN202211559665.7A CN118146805A (en) | 2022-12-06 | 2022-12-06 | Diphenyl thiophene liquid crystal compound and its preparation method and application |
| PCT/CN2023/132110 WO2024120149A1 (en) | 2022-12-06 | 2023-11-16 | Dibenzothiophene liquid crystal compound, and preparation method therefor and use thereof |
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| CN112980458B (en) * | 2019-12-13 | 2022-07-22 | 北京八亿时空液晶科技股份有限公司 | Bridged naphthene-containing liquid crystal compound and preparation method and application thereof |
| CN113881443A (en) * | 2020-07-01 | 2022-01-04 | 北京八亿时空液晶科技股份有限公司 | Liquid crystal compound containing dibenzothiophene structure and application thereof |
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| CN114105941B (en) * | 2020-08-27 | 2024-03-08 | 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 |
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