CN103555344B - Liquid crystal compound containing tetrahydro-thiopyran group and preparation method thereof, and liquid crystal composition - Google Patents
Liquid crystal compound containing tetrahydro-thiopyran group and preparation method thereof, and liquid crystal composition Download PDFInfo
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 161
- 150000001875 compounds Chemical class 0.000 title claims abstract description 90
- 239000000203 mixture Substances 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 62
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical group C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 title abstract 2
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims description 157
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 108
- 239000002904 solvent Substances 0.000 claims description 101
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 84
- 238000001704 evaporation Methods 0.000 claims description 73
- 239000012044 organic layer Substances 0.000 claims description 73
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 73
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 60
- 239000000376 reactant Substances 0.000 claims description 51
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 41
- 239000012043 crude product Substances 0.000 claims description 36
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 32
- 125000004432 carbon atom Chemical group C* 0.000 claims description 32
- 238000010438 heat treatment Methods 0.000 claims description 32
- 239000000463 material Substances 0.000 claims description 29
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 28
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 27
- 239000012467 final product Substances 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 23
- 238000010992 reflux Methods 0.000 claims description 23
- 238000000926 separation method Methods 0.000 claims description 20
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 17
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 claims description 14
- 238000000605 extraction Methods 0.000 claims description 13
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 238000004440 column chromatography Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 9
- 125000003342 alkenyl group Chemical group 0.000 claims description 8
- 125000003545 alkoxy group Chemical group 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000001953 recrystallisation Methods 0.000 claims description 7
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 230000004224 protection Effects 0.000 claims description 6
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- JOOMLFKONHCLCJ-UHFFFAOYSA-N N-(trimethylsilyl)diethylamine Chemical compound CCN(CC)[Si](C)(C)C JOOMLFKONHCLCJ-UHFFFAOYSA-N 0.000 claims description 5
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 claims description 5
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 claims description 4
- ZRTWIJKGTUGZJY-UHFFFAOYSA-N 3,4,5-trifluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1 ZRTWIJKGTUGZJY-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 claims description 4
- 239000005457 ice water Substances 0.000 claims description 4
- 238000006722 reduction reaction Methods 0.000 claims description 4
- BTTUMVHWIAXYPJ-UHFFFAOYSA-N 1,3-dithian-2-yl(trimethyl)silane Chemical compound C[Si](C)(C)C1SCCCS1 BTTUMVHWIAXYPJ-UHFFFAOYSA-N 0.000 claims description 3
- QDFKKJYEIFBEFC-UHFFFAOYSA-N 1-bromo-3-fluorobenzene Chemical compound FC1=CC=CC(Br)=C1 QDFKKJYEIFBEFC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009903 catalytic hydrogenation reaction Methods 0.000 claims description 3
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 abstract description 6
- 239000000178 monomer Substances 0.000 abstract description 5
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 abstract description 3
- 239000000543 intermediate Substances 0.000 description 77
- 239000000243 solution Substances 0.000 description 33
- 238000012360 testing method Methods 0.000 description 27
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- 125000001309 chloro group Chemical group Cl* 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 0 CC(CCC(C)C(C)(C)*)C(C)CCC(C(CC1)=CC=C1Br)S Chemical compound CC(CCC(C)C(C)(C)*)C(C)CCC(C(CC1)=CC=C1Br)S 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 5
- 239000007858 starting material Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 125000003302 alkenyloxy group Chemical group 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical group [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052801 chlorine Chemical group 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000013213 extrapolation Methods 0.000 description 2
- 239000011737 fluorine Chemical group 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- HGBOYTHUEUWSSQ-UHFFFAOYSA-N pentanal Chemical compound CCCCC=O HGBOYTHUEUWSSQ-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- FTHJRZWIHWGZSJ-UHFFFAOYSA-N 5-propyloxan-2-one Chemical compound CCCC1CCC(=O)OC1 FTHJRZWIHWGZSJ-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical class C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- IGARGHRYKHJQSM-UHFFFAOYSA-N cyclohexylbenzene Chemical class C1CCCCC1C1=CC=CC=C1 IGARGHRYKHJQSM-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000020061 kirsch Nutrition 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a liquid crystal compound containing a tetrahydro-thiopyran group and a preparation method thereof and a liquid crystal composition. The liquid crystal compound is represented by a general formula I. The liquid crystal composition comprises no more than 40% but more than 0 of the compound as represented by the general formula I, 4 to 50% of a compound as represented by a general formula II, 5 to 50% of a compound as represented by a general formula III and 3 to 45% of a compound as represented by a general formula IV. The liquid crystal compound provided by the invention has low rotary viscosity gamma 1, great dielectric anisotropy, a wide nematic phase temperature range, good intermiscibility, light stability and thermal stability and is fairly applicable as a liquid crystal monomer; the liquid crystal composition containing the liquid crystal compound has a great liquid crystalline phase temperature range, appropriate optical anisotropy, small rotary viscosity and low starting voltage and is especially applicable to liquid crystal display elements of a TN mode, a VA mode, an IPS mode and a PDLC mode.
Description
Technical Field
The invention relates to a liquid crystal compound containing a thiotetrahydropyranyl group, a preparation method thereof and a liquid crystal composition containing the liquid crystal compound, belonging to the field of liquid crystal compounds and application thereof.
Background
In recent years, liquid crystal displays have replaced the conventional cathode ray tube displays, become mainstream products in the information display field, and are widely used in various displays such as instruments, computers, televisions, and the like. Liquid crystal display elements can be classified into various modes such as a Twisted Nematic (TN) mode, a Super Twisted Nematic (STN) mode, an in-plane switching (IPS) mode, and a Vertical Alignment (VA) mode, depending on the liquid crystal display mode.
A Thin Film Transistor Liquid Crystal Display (TFT-LCD), which is one of the most promising Display technologies in the 21 st century, has been widely used in the fields of notebook computers, Liquid Crystal televisions, etc. The TFT-LCD is an active matrix display formed by introducing a thin film transistor switch on the basis of a twisted nematic liquid crystal display (TN-LCD), overcomes the defects of cross interference, less information content, low writing speed and the like in passive matrix display, greatly improves the display quality and is rapidly developed.
The advantages of TFT-LCDs can be summarized as the following five points: the use characteristics are good: low voltage applications, low drive voltages; the board is flat, light and thin, and a large amount of raw materials and use space are saved; low power consumption; the display quality is from the simplest monochromatic character and figure to the video display with various specifications and models, such as high resolution, high color fidelity, high brightness, high contrast and high response speed; the display modes include various display modes such as a direct-view mode, a projection mode, a see-through mode, a reflection mode and the like. Secondly, the environmental protection characteristic is good: the TFT-LCD has no radiation and flicker, has no harm to the health of users, particularly the appearance of TFT-LCD electronic books and periodicals, brings human beings into paperless office and paperless printing era, and initiates the revolution of learning, spreading and recording civilization modes of the human beings. The application range is wide: the TFT-LCD can be normally used within the range of-20 ℃ to 50 ℃, and the low-temperature working temperature of the TFT-LCD subjected to temperature reinforcement treatment can even reach-80 ℃. The TFT-LCD can be used as a mobile terminal display and a desktop terminal display, can also be used as a large-screen projection television, and is a full-size video display terminal with excellent performance. And fourthly, the automation degree of the manufacturing technology is high. The TFT-LCD is easy to integrate and update.
The liquid crystal material is one of important photoelectronic materials for liquid crystal displays, and plays an important role in improving the performance of the liquid crystal displays. Liquid crystal materials for display use are all required to satisfy the following properties: the chemical, physical and thermal stability is good, and the stability to electric fields and electromagnetic radiation is good; ② the viscosity (gamma 1) is low; ③ has proper dielectric anisotropy delta; fourthly, proper optical anisotropy delta n; fifthly, the compatibility with other liquid crystal compounds is good. The liquid crystal material for the TFT-LCD has higher requirements than the common liquid crystal material, and in addition to the characteristics, the liquid crystal material also has the properties of wider nematic phase temperature range, very high resistivity, good ultraviolet resistance, high charge retention rate, low vapor pressure, low ion concentration, low power consumption, low rotational viscosity and the like.
The liquid crystal material is one of important photoelectronic materials for liquid crystal displays, and plays an important role in improving the performance of the liquid crystal displays. As a liquid crystal material for display, a wide nematic phase temperature range, high stability, suitable rotational viscosity, and fast response to an electric field are required. However, so far, no single liquid crystal compound has been found to meet the above performance requirements, and a plurality of liquid crystal compounds must be combined into a liquid crystal composition to meet the performance requirements of the liquid crystal display material.
In order to satisfy the requirements of display performance such as TN mode, STN mode, TFT-LCD, etc., liquid crystal compounds for display have been developed from liquid crystal compounds containing biphenylnitriles, esters, oxygen-containing heterocycles and pyrimidine rings to liquid crystal compounds containing cyclohexylbenzenes, phenylacetylenes, ethyl bridges, terminal alkenyls and various fluorine-containing aromatic rings.
Among them, fluorine-containing liquid crystals are the main component of liquid crystal materials for TFT liquid crystal displays because of their properties such as low viscosity, moderate dielectric anisotropy, high resistivity, and high charge retention rate. Introducing a difluoromethyleneoxy bridge (-CF) into liquid crystal molecules2O-) expands its nematic phase temperature range to a large extent and at the same time has a rotational viscosity of gamma1Is also reduced. In addition, due to the difluoromethyleneoxy bridge (-CF)2O-) and the dipole moment of the terminal fluorine atom to a certain extent, thereby increasing the dielectric anisotropy Delta of the liquid crystal molecules. Germany Merck and Japanese Kohyo corporation have disclosed several difluoromethyleneoxy bridges (-CF) with different substituents2O-) and liquid crystal compounds (CN 1717468A, CN101143808A, CN101157862A, etc.) and applied to the liquid crystal composition.
With the continuous development of the liquid crystal display industry, the demand of people for display materials with different properties is increasing. Therefore, the development of new liquid crystal compounds and compositions having excellent properties is becoming important for the development of liquid crystal displays.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a liquid crystal compound containing thiotetrahydropyranyl and a liquid crystal composition thereof, which are suitable for a liquid crystal display and have higher stability, wider nematic phase range, lower rotational viscosity and high dielectric anisotropy.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
the liquid crystal compound containing the thiotetrahydropyranyl has a structure shown in a general formula I:
wherein R is1、R2Is any one of the following groups:
①-H、-Cl、-F、-CN、-OCN、-OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-SCN、-NCS、-SF5；
② alkyl containing 1 to 15 carbon atoms, alkoxy containing 1 to 15 carbon atoms, alkenyl containing 2 to 15 carbon atoms and alkenyloxy containing 2 to 15 carbon atoms;
③ one or more non-adjacent-CH2-by-CH = CH-, -C ≡ C-, -COO-, -OOC-,a group represented by the above-mentioned (II) wherein the oxygen atom in the group after the substitution is not directly bonded;
(iv) any H atom is substituted by fluorine atom or chlorine atom;
each is a single bond or any one of the following groups:
Z1、Z2are each a single bond, -CH2-、-CH2CH2-、-(CH2)3-、-(CH2)4-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-or-CF = CF-;
n1、n2、n3、n4is any one of the values 0, 1, 2 or 3, respectively, and n1+n2+n3+n4≤5。
The liquid crystal composition comprises at least one compound shown as a general formula I, wherein the weight percentage of the compound shown as the general formula I in the liquid crystal composition is less than or equal to 40% and is not zero; the liquid crystal composition also comprises 4 to 50 weight percent of compound shown in a general formula II, 5 to 50 weight percent of compound shown in a general formula III and 3 to 45 weight percent of compound shown in a general formula IV,
wherein,
R3、R4、R5、R6、R7respectively is any one of-CN, -F, alkyl with 1 to 7 carbon atoms, alkoxy with 1 to 7 carbon atoms, alkenyl with 2 to 7 carbon atoms or fluoro alkoxy with 1 to 5 carbon atoms;
Z3、Z4are each a single bond, -CH2CH2-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2Any one of (1) to (1);
are each a single bond or lowerAny one of the following groups:
Y1、Y2are-H or-F, respectively;
n5、n6each is 0, 1, or 2.
Due to the adoption of the technical scheme, the technical progress of the invention is as follows:
the invention discloses a liquid crystal compound containing a thiotetrahydropyranyl, which has stable structure, general physical properties required by liquid crystal materials, light and heat stability, wider nematic phase temperature range and good compatibility with other compounds, particularly has low rotary viscosity gamma 1 and large dielectric anisotropy (delta > 0), is very suitable for being used as a liquid crystal monomer for liquid crystal display, and is particularly suitable for preparing TN mode, VA mode, IPS mode or PDLC mode liquid crystal displays. When the compound is used in a liquid crystal composition, the optical anisotropy of the liquid crystal composition can be effectively adjusted, so that the threshold voltage and the rotational viscosity of the liquid crystal composition are reduced, the response time is shortened, and the performance of the liquid crystal composition is obviously optimized.
The invention also provides a preparation method of the liquid crystal compound containing the thiotetrahydropyranyl, and the liquid crystal compound has the advantages of simple synthetic route, easy operation, higher reaction yield and low production cost; the use of the liquid crystal composition can reduce the preparation cost of the liquid crystal composition, and has good industrial prospect.
The invention also provides a liquid crystal composition which comprises at least one compound shown in the general formula I, at least one compound shown in the general formula II, at least one compound shown in the general formula III and at least one compound shown in the general formula IV. The liquid crystal composition has a large liquid crystal phase temperature range and proper optical anisotropy, is small in rotational viscosity and low in starting voltage, is suitable for various liquid crystal displays, electro-optical displays and electro-optical liquid crystal displays, is particularly suitable for TN type displays, VA type displays, IPS type displays or PDLC type displays, and has wide application prospect and market value.
Detailed Description
The present invention will be described in further detail with reference to the following examples:
the percentages referred to in the following examples are percentages by weight, the temperature unit is, the specific meanings of other symbols and the test conditions are as follows:
HPLC for high performance liquid chromatography purity (%), test equipment: model HP1100 high performance liquid chromatograph from Agilent;
GC represents high performance gas chromatography purity (%), test instrument: an HP6820 gas chromatograph of Agilent;
GC-MS indicates gas mass spectroscopy, test instrument: aeronautical spectrometer model MS5975C from agilent corporation;
1H-HMR represents nuclear magnetic hydrogen spectrum, and the test instrument: DRX-500 NMR, Bruker Biospin Corp;
m.p. denotes melting point, test instrument: WRX-1S micro thermal analyzer, test conditions: the temperature rising speed is 3 ℃/min;
p. shows the clearing point (. degree. C.) of the liquid crystal, the test apparatus: a melting point instrument FP-52 type manufactured by Mettler company, and the temperature rising speed is 3 ℃/min; ② DSC822E model differential thermal torsion scanner of Mettler company, temperature rising speed is 1 ℃/min;
Δ n denotes optical anisotropy, Δ n = no-neWherein n isoRefractive index of ordinary light, neFor the refractive index of the extraordinary rays, the test instrument: abbe refractometer, test conditions: 589nm、25℃；
Δ represents dielectric anisotropy, Δ =∥-⊥Wherein∥is the dielectric constant parallel to the molecular axis,⊥for dielectric constant perpendicular to the molecular axis, the instrument was tested: HP4284A model precision LCR tester from hewlett packard company, test conditions: 25 ℃;
γ 1 represents rotational viscosity (mPa · s), test instrument: model6254 liquid crystal parameter comprehensive tester of TOYO corporation of japan, test conditions: 20 +/-0.5 ℃.
A liquid crystal compound containing a thiotetrahydropyranyl group has a structure shown as a general formula I:
wherein R is1、R2Is any one of the following groups:
①-H、-Cl、-F、-CN、-OCN、-OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-SCN、-NCS、-SF5；
② alkyl containing 1 to 15 carbon atoms, alkoxy containing 1 to 15 carbon atoms, alkenyl containing 2 to 15 carbon atoms and alkenyloxy containing 2 to 15 carbon atoms;
③ one or more non-adjacent-CH2-by-CH = CH-, -C ≡ C-, -COO-, -OOC-,a group represented by the above-mentioned (II) wherein the oxygen atom in the group after the substitution is not directly bonded;
(iv) any H atom is substituted by fluorine atom or chlorine atom;
R1preferably selected from-H, containing 1 to 15Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms;
R2preferably selected from-H, -Cl, -F, -CN, -OCN, -OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-SCN、-NCS、-SF5Any one of an alkyl group having 1 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, and an alkenyloxy group having 2 to 15 carbon atoms;
each is a single bond or any one of the following groups:
Z1、Z2are each a single bond, -CH2-、-CH2CH2-、-(CH2)3-、-(CH2)4-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-CF2CF2-or-CF = CF-;
Z1、Z2preferably from single bonds, -CH2-、-CH2CH2-、-(CH2)3-、-(CH2)4-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2Any one of (1) to (1);
n1、n2、n3、n4is any one of the values 0, 1, 2 or 3, respectively, and n1+n2+n3+n4≤5。
The liquid crystal compound is preferably any one of compounds represented by formula I-1 to formula I-7,
wherein,
R1is-H or a straight-chain alkyl group having 1 to 10 carbon atoms, preferably-H or a straight-chain alkyl group having 1 to 6 carbon atoms;
R2is-F, -Cl, -OCF3、-CF3、-CN、-NCS、-OCHF2Any of the groups in (1), preferably is-F, -Cl, -OCF3、-CF3Any one of the groups of-CN, -NCS;
L1、L2、L3、L4、L5、L6、L7、L8is-H or-F, respectively.
The preferred liquid-crystalline compounds of formula I-1 are most preferably selected from the following compounds:
the preferred liquid crystal compounds of formula I-4 are most preferably selected from the following:
the preferred liquid crystal compounds of formula I-5 are most preferably selected from the following:
the preferred liquid crystal compounds of formula I-7 are most preferably selected from the following:
liquid crystal compounds containing a thiotetrahydropyranyl group represented by the general formula I can be prepared by known chemical synthesis methods, which are described in the following references:
（1）B Ekkehard,H Reinhard,K Hansadolf et al.US:5045229,1991.；
（2）M.Kuroboshi et al.，Chem.Lett.,1992,827；
（3）W.H.Bunnelle et al.,J.Org.Chem.1990,55,768.；
（4）Peer.Kirsch et al.,Angew.Chem.Int.Ed.2001.40，1480-1484.。
the preferred compounds of formula I-1, formula I-2, formula I-3, formula I-4, formula I-5, formula I-6, and formula I-7 are prepared by a process selected from the following three routes:
when preparing compounds of formula I-1, formula I-2, formula I-3, scheme A is used:
the specific conditions of the reactions in the steps of the route A are respectively as follows:
preparation of intermediate b:
putting reaction raw materials a, reactants of methyl acrylate, trimethylsilyl diethylamine, p-hydroxyanisole and solvent of acetonitrile into a reactor, and carrying out reflux reaction under the protection of nitrogen; after the reaction is finished, evaporating the solvent, adding glacial acetic acid and water, and continuing to perform reflux reaction; cooling after the reaction is finished, and adding methyl tert-butyl ether for extraction and liquid separation; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
adding a solvent methanol into the evaporated material, and adding sodium borohydride at the controlled temperature of 0-10 ℃ to perform reduction reaction; after the reaction is finished, adding water and methyl tert-butyl ether for extraction and liquid separation, and evaporating the solvent in the organic layer to dryness to obtain a secondary evaporated material;
adding catalyst p-toluenesulfonic acid and solvent toluene into the secondary evaporated material, and carrying out reflux reaction; after the reaction is finished, adding water and toluene for extraction and liquid separation, evaporating the solvent in the organic layer to dryness to obtain an intermediate b crude product, and refining to obtain an intermediate b;
preparation of intermediate c:
putting the intermediate b, a reactant trimethyl silicon iodide and a solvent dichloromethane into a reactor, and reacting at 25 +/-5 ℃; adding water after the reaction is finished, and separating liquid; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
adding reactant oxalyl chloride and solvent benzene into the steamed dry matter, and stirring for reaction at 25 +/-5 ℃; after the reaction is finished, evaporating the solvent, adding dichloromethane and triethylamine, and then introducing hydrogen sulfide gas into the reaction solution for reaction; adding a sodium bicarbonate solution after the reaction is finished, and separating liquid; evaporating the solvent in the organic layer to dryness to obtain an intermediate c;
preparation of intermediate d:
controlling the temperature to be minus 50 +/-5 ℃, dripping reactant butyl lithium into tetrahydrofuran solution containing 1, 4-dibromobenzene, continuously dripping the tetrahydrofuran solution of the intermediate c after dripping, and stirring for reaction; adding water for separating liquid after the reaction is finished; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
dissolving the evaporated material in dichloromethane, dripping reactants triethylsilane and boron trifluoride diethyl etherate at-75 +/-5 ℃, and keeping the temperature for reaction; after the reaction is finished, heating, adding saturated sodium bicarbonate solution for hydrolysis, and then extracting and separating liquid; evaporating the solvent in the organic layer to dryness to obtain a crude product of an intermediate d; recrystallizing to obtain an intermediate d;
preparation of intermediate e:
controlling the temperature to be-75 +/-5 ℃, dropping reactant butyl lithium into the tetrahydrofuran solution containing the intermediate d, and continuing dropping the tetrahydrofuran solution of reactant trimethyl borate after dropping; after the dropwise addition is finished, heating to-20 +/-5 ℃, adding hydrochloric acid, stirring for reaction, and extracting and separating liquid after the reaction is finished; evaporating the solvent in the organic layer to dryness to obtain an intermediate e crude product, and recrystallizing to obtain an intermediate e;
preparation of intermediate f:
adding tetrahydrofuran, water and hydrogen peroxide into the intermediate e, and reacting at 40 +/-5 ℃; after the reaction is finished, adding water and dichloromethane for liquid separation, evaporating the solvent in the organic layer to dryness to obtain an intermediate f crude product, and recrystallizing to obtain an intermediate f;
preparation of intermediate g:
adding 5% palladium carbon and solvent toluene into the intermediate f, and carrying out catalytic hydrogenation reaction at 25 + -5 deg.C and 0.25 + -0.05 Mpa; after the reaction is finished, filtering out the catalyst, and evaporating the solvent to dryness to obtain an intermediate g;
preparation of intermediate h:
controlling the temperature to be-75 +/-5 ℃, dropping reactant butyl lithium into tetrahydrofuran solution containing reactant 2-trimethylsilyl-1, 3-dithiane, and slowly raising the temperature to 0 ℃ after dropping; then cooling to-75 +/-5 ℃ again, and dripping tetrahydrofuran solution containing the intermediate g; after the dropwise addition is finished, heating to-25 +/-5 ℃, and continuously stirring for reaction; after the reaction is finished, adding water for liquid separation, evaporating the solvent in the organic layer to dryness to obtain a crude product of an intermediate h, and recrystallizing to obtain the intermediate h;
preparation of final product I:
temperature control-20Dripping the reactant trifluoromethanesulfonic acid into a dichloromethane solution containing the intermediate h at +/-5 ℃, stirring for reacting for 30min, and continuously cooling to-75 +/-5 ℃; under the condition of the temperature, firstly, a dichloromethane solution containing reactants 3,4, 5-trifluorophenol and triethylamine is dripped in, and then the reactant NEt is added rapidly33 HF; controlling the temperature to be-75 +/-5 ℃, dripping dichloromethane solution containing liquid bromine, and continuously stirring for reaction at the temperature; after the reaction is finished, heating to 0 +/-5 ℃, pouring the reaction liquid into an ice-water mixture, adjusting the pH value of the reactant system to 5-8 by using a sodium hydroxide solution, and then separating liquid; and (3) evaporating the solvent in the organic layer to dryness to obtain a crude product of the final product I, and performing column chromatography and recrystallization to obtain the final product I.
When L in the formulae I-4 and I-65、L6All are-H, L in formula I-5 or formula I-77、L8When all are-H, the synthesis is carried out using route B:
the specific conditions of the reactions in the steps of the route B are respectively as follows:
process for preparing intermediate e from starting material a the same procedure as for preparing intermediate e from starting material a in scheme a;
preparation of final product I:
adding reactants to intermediate eHeating up catalysts of palladium tetratriphenylphosphine, sodium carbonate, solvents of toluene, ethanol and water for reflux reaction; after the reaction is finished, adding water for separating liquid, and evaporating the solvent in the organic layer to dryness to obtain a crude product of a final product I; and (4) carrying out column chromatography and recrystallization to obtain a final product I.
When L in the formulae I-4 and I-65、L6At least one of the groups is-F, L in the formulae I-5 and I-77、L8When at least one is-F, the synthesis is carried out using scheme C:
the specific conditions of the reactions in the steps of the route C are respectively as follows:
process for preparing intermediate c from starting material a the process for preparing intermediate c from starting material a in scheme a;
preparation of intermediate d':
controlling the temperature to be minus 50 +/-5 ℃, dripping reactant butyl lithium into tetrahydrofuran solution containing 3-bromofluorobenzene, continuously dripping the tetrahydrofuran solution of the intermediate c after dripping, and stirring for reaction; adding water for separating liquid after the reaction is finished, and evaporating the solvent in the organic layer to dryness to obtain a dried substance;
dissolving the evaporated material in dichloromethane, dripping reactants triethylsilane and boron trifluoride diethyl etherate at-75 +/-5 ℃, and reacting at the temperature; after the reaction is finished, heating, adding saturated sodium bicarbonate solution for hydrolysis, separating liquid, and evaporating the solvent in the organic layer to dryness to obtain an intermediate d';
preparation of intermediate e':
controlling the temperature to be minus 95 +/-5 ℃, dropping reactant butyl lithium into tetrahydrofuran solution containing intermediate d' and potassium tert-butoxide, and continuing dropping the tetrahydrofuran solution of reactant trimethyl borate after dropping; after the dropwise addition is finished, heating to-20 +/-5 ℃, adding hydrochloric acid and water, and stirring for reaction for 30 min; after the reaction is finished, separating liquid, and evaporating the solvent in the organic layer to dryness to obtain an intermediate e';
preparation of final product I:
addition of reactants to intermediate eCatalyst tetratriphenylphosphine palladium and sodium carbonateHeating and refluxing the solvent toluene, ethanol and water for reaction; after the reaction is finished, adding water for separating liquid, and evaporating the solvent in the organic layer to dryness to obtain a crude product of a final product I; and (4) carrying out column chromatography and recrystallization to obtain a final product I.
The liquid crystal composition comprises at least one compound shown as a general formula I, wherein the weight percentage of the compound shown as the general formula I in the liquid crystal composition is less than or equal to 40% and is not zero; also comprises 4 to 50 weight percent of compound shown in a general formula II, 5 to 50 weight percent of compound shown in a general formula III and 3 to 45 weight percent of compound shown in a general formula IV,
wherein,
R3、R4、R5、R6、R7respectively is any one of-CN, -F, alkyl with 1 to 7 carbon atoms, alkoxy with 1 to 7 carbon atoms, alkenyl with 2 to 7 carbon atoms or fluoro alkoxy with 1 to 5 carbon atoms;
Z3、Z4are each a single bond, -CH2CH2-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2Any one of (1) to (1);
each is a single bond or any of the following groups:
Y1、Y2are-H or-F, respectively;
n5、n6each is 0, 1, or 2.
The liquid crystal composition preferably comprises 8-19 wt% of a liquid crystal compound shown in a general formula I, 20-36 wt% of a liquid crystal compound shown in a general formula II, 31-47 wt% of a liquid crystal compound shown in a general formula III and 5-33 wt% of a liquid crystal compound shown in a general formula IV.
The starting materials used in the following examples, unless otherwise specified, were all publicly available commercially.
The following examples give products of the general formula I which are tested in two ways:
1) test m.p., c.p., HPLC, GC, MS, 1H-NMR with itself as a sample;
2) the product was mixed with a mother liquid crystal as a sample, and the mixture was prepared according to the handbook of liquid crystal devices (author: japanese academy 142 committee) for testing Δ, Δ n; the specific test method comprises the following steps: firstly, mixing 15% of liquid crystal product and 85% of mother liquid crystal to prepare a sample for testing, and then calculating an extrapolation value through an extrapolation method according to a test value of the obtained sample, namely the performance data of the prepared product. The extrapolated value is calculated as: extrapolated value = [100 × (test value of sample) - (weight% of mother liquid crystal) × (test value of mother liquid crystal) ]/weight% of compound.
The matrix liquid crystal used had the following composition:
example 1
Preparation of compound I-a:
the synthetic route is as follows:
the preparation method comprises the following specific steps:
1.1 preparation of intermediate I-a-1:
adding 9.5g (0.11 mol) of n-valeraldehyde, 9.5g (0.11 mol) of methyl acrylate, 16g (0.11 mol) of trimethylsilyl diethylamine, 1g of p-hydroxyanisole and 130ml of acetonitrile (solvent) into a 250ml reaction bottle, heating to reflux under the protection of nitrogen, and carrying out reflux reaction for 24 hours; cooling after the reaction is finished, and evaporating to remove the solvent; then adding 22ml of glacial acetic acid and 44ml of water into the reaction bottle, heating again, and carrying out reflux reaction for 2 h; after the reaction is finished, cooling to room temperature, adding 100ml of methyl tert-butyl ether and 100ml of water, and extracting and separating liquid; the aqueous layer was extracted with 50ml of 2 methyl tert-butyl ether (i.e. each time with 50ml of methyl tert-butyl ether, 2 times in total; the same applies below), and the organic layers were combined; washing the organic layer with water, then washing the organic layer with 50ml of sodium bicarbonate aqueous solution to neutrality, adding anhydrous sodium sulfate and drying; the drying agent was filtered off and the solvent was evaporated to dryness to give 13.4g of a red liquid (GC: 86.8%);
putting 13.4g of the obtained red liquid and 60ml of anhydrous methanol into a 100ml reaction bottle, and cooling in an ice-water bath; under the condition that the reaction temperature is controlled to be less than 10 ℃, 1.35g (0.0345 mol, 0.5 eq) of sodium borohydride is added for multiple times, and stirring reaction is continued for 30min after the addition; the ice water bath was then removed, slowly warmed to room temperature, and the reaction was stirred at room temperature for 1 h. After the reaction is finished, adding 100ml of methyl tert-butyl ether and 100ml of water into a reaction bottle, and extracting and separating liquid; the aqueous layer was extracted with 50ml × 2 methyl tert-butyl ether, the organic layers were combined and washed with water; evaporating the solvent to dryness to obtain 13g of yellow liquid;
putting 13g of the obtained yellow liquid, 0.1g of p-toluenesulfonic acid and 100ml of toluene into a 250ml reaction bottle provided with a water separator, heating, and reacting at 110 ℃ for 2 h; after most of the methanol is completely evaporated, raising the reaction temperature to 120 ℃, and continuing the reaction; after 50ml of reaction liquid is distilled out, adding 50ml of toluene, then distilling out 50ml of reaction liquid again, stopping heating and slowly cooling; adding 100ml toluene and 100ml water for extraction and liquid separation, washing the organic layer with water, evaporating the solvent, and refining with silica gel column (eluent is petroleum ether: methyl tert-butyl ether =4: 1) to obtain 8.3g of intermediate I-a-1 (5-propyltetrahydropyran-2-one); the yield is 72.4%; GC: 85 percent.
1.2 preparation of intermediate I-a-2
Adding 14.2g (0.1mol) of intermediate I-a-1, 100ml of dichloromethane and 21g (0.105 mol) of trimethyl silicon iodide into a reaction bottle, and stirring at 25 +/-5 ℃ for reaction for 10 hours; after the reaction is finished, 100ml of water is added for extracting and separating liquid, and an organic layer is separated; after the aqueous layer was extracted with dichloromethane, the organic layers were combined and washed with 50ml × 4 water; adding 20g of anhydrous sodium sulfate into the organic layer, drying for 2h, filtering out a drying agent, and evaporating the solvent to dryness;
adding 100ml benzene into the steamed dry matter for dissolving, then adding 50.8g (0.4 mol) oxalyl chloride, and stirring and reacting for 10h at 25 +/-5 ℃; after the reaction is finished, evaporating the solvent, adding 100ml of dichloromethane and 300ml of triethylamine into the evaporated material, and introducing 5.1g (0.15 mol) of hydrogen sulfide gas into the mixture to react under stirring; after the reaction is completed, adding 500ml of saturated ammonium chloride solvent for liquid separation, and separating an organic layer; after the aqueous layer was extracted with 100ml of 2 dichloromethane, the organic layers were combined and dried by adding 50g of anhydrous sodium sulfate; filtering out a drying agent, and evaporating the solvent to dryness to obtain 79g of evaporated matter, namely the intermediate I-a-2; the yield thereof was found to be 50%.
1.3 preparation of intermediate I-a-3
Adding 23.6g (0.1mol) of 1, 4-dibromobenzene and 250ml of tetrahydrofuran into a reaction bottle, stirring and dissolving, cooling to-60 to-50 ℃, and dropwise adding 40ml of 2.5M (0.1mol) of butyllithium under the condition that the system temperature is not higher than-50 ℃; then, 15.8g (0.1mol) of tetrahydrofuran solution of the intermediate I-a-2 is continuously dripped (15.8 g of the intermediate I-a-2 is dissolved in 50ml of tetrahydrofuran), and the mixture is stirred and reacted for 30min after dripping; naturally heating to-20 ℃, adding 50ml of water for separating, discarding a water layer, washing an organic layer with 50ml of multiplied by 4 water, and evaporating the solvent to obtain a crude product;
dissolving the crude product in 40ml of dichloromethane, and cooling to-85 to-75 ℃; controlling the temperature to be not higher than-70 ℃, firstly adding 40ml of triethylsilane, then dropwise adding 40ml of boron trifluoride ethyl ether solution, and stirring and reacting for 1h after dropwise adding; after the reaction is finished, heating to-10 ℃, adding a saturated sodium bicarbonate solution for hydrolysis, and separating liquid; the aqueous phase was extracted with 20ml dichloromethane and the organic layers were combined; washing the organic layer twice with 40ml of water, and then evaporating the solvent in the organic layer to dryness to obtain a product containing a 9:1 cis-trans isomer; recrystallizing the product with hexane at-20 deg.C to obtain 15g of final product, i.e. intermediate I-a-3; the yield thereof was found to be 50%.
1.4 preparation of intermediate I-a-4
Dissolving 29.9g (0.1mol) of the intermediate I-a-3 in 200ml of tetrahydrofuran, and cooling to-80 to-70 ℃; 40ml of 2.5 molar butyllithium (0.1mol) are added dropwise, and then 13.5g (0.13mol) of a tetrahydrofuran solution of trimethyl borate are added dropwise (13.5 g of trimethyl borate is dissolved in 50ml of tetrahydrofuran); after the dropwise addition, slowly heating the mixture to-20 ℃, adding 100ml of 2N hydrochloric acid, and stirring for reaction for 1 h; after the reaction is finished, liquid separation is carried out, the water phase is extracted by 100ml of ethyl acetate, the organic layers are combined and washed by 100ml of multiplied by 2 water, and the solvent in the organic layers is evaporated to dryness to obtain a crude product of the intermediate I-a-4; recrystallizing the crude product in n-heptane to obtain 18.5g of a final product, namely the intermediate I-a-4; the yield is 70%; HPLC: 97 percent.
1.5 preparation of intermediate I-a-5
Adding 26.5g (0.1mol) of intermediate I-a-4, 300ml of tetrahydrofuran, 50ml of water and 30ml of 30% hydrogen peroxide into a reaction bottle, and stirring and reacting for 2 hours at the temperature of 40 +/-5 ℃; after the reaction is finished, adding 100ml of dichloromethane and 200ml of water into a reaction bottle, stirring for 10min, separating liquid, separating an organic layer, extracting a water layer by using 100nl of dichloromethane, and combining the organic layers; then washing the organic layer to neutrality by using water, and evaporating the solvent to obtain a crude product; recrystallizing the crude product with 2 times of ethanol to obtain 19g of a final product, namely an intermediate I-a-5; the yield thereof was found to be 80%.
1.6 preparation of intermediate I-a-6
Dissolving 23.7g (0.1mol) of the intermediate I-a-5 in 200ml of toluene, adding 5g of 5% palladium-carbon catalyst, and carrying out catalytic hydrogenation for 10h under the pressure of 0.25 MPa; filtering the catalyst, and evaporating the solvent to dryness to obtain 23g of a product, namely an intermediate I-a-6; the yield thereof was found to be 95.4%.
1.7 preparation of intermediate I-a-7
Adding 19.2g (0.1mol) of 2-trimethylsilyl-1, 3-dithiane and 75ml of tetrahydrofuran into a reaction bottle, and cooling to-80 to-70 ℃ after dissolving; 40m2.5M (0.1mol) butyl lithium is dropped into the mixture under the condition that the temperature is controlled to be not higher than-70 ℃; after the dripping is finished, heating the system to 0 ℃ within 4h, then cooling to-70 ℃ to-80 ℃ again, dripping 24.1g (0.1mol) of tetrahydrofuran solution of the intermediate I-a-6 (dissolving 24.1g of the intermediate I-a-6 in 250ml of tetrahydrofuran), slowly heating to room temperature after the dripping is finished, and stirring and reacting for 18h at the temperature of 25 +/-5 ℃; after the reaction is finished, adding 100ml of water for separating liquid, removing a water layer, drying an organic layer, and evaporating to dryness to obtain a crude product; recrystallizing the crude product with n-heptane to obtain white crystals 20.6g, namely intermediate I-a-7; the yield thereof was found to be 60%.
1.8 preparation of Compounds I-a
Adding 34.3g (0.1mol) of intermediate I-a-7 and 50ml of dichloromethane into a reaction bottle, stirring and dissolving, and then cooling to-30 to-20 ℃; 15g of (A) is added dropwise under the condition that the temperature is controlled to be not higher than-20 DEG C0.1mol) of trifluoromethanesulfonic acid, and stirring to react for 30min after dripping; then the temperature is reduced to-70 ℃ to-80 ℃, a dichloromethane solution of 19.2g (0.13mol) of 3,4, 5-trifluorophenol and 30.3g (0.3mol) of triethylamine is firstly dropped (19.2 g of 3,4, 5-trifluorophenol and 30.3g of triethylamine are dissolved in 20ml of dichloromethane), and then 63.2g (0.4 mol) of NEt is added within 5min33 HF; then, under the condition that the temperature is controlled to be not higher than-70 ℃, adding 64g (0.4 mol) of a dichloromethane solution of bromine (64 g of bromine is dissolved in 30ml of dichloromethane) within 1h, and after the addition is finished, controlling the temperature below-70 ℃ and stirring for reaction for 1 h;
after the reaction is finished, heating to 0 ℃, pouring the reaction solution into 160ml of 32% sodium hydroxide solution and 300g of ice, dropwise adding 32% sodium hydroxide solution to adjust the pH value of the system to 5-8, and consuming about 45g of 32% sodium hydroxide solution; standing, separating organic layers, extracting the water layer with 80ml dichloromethane, and combining the organic layers; adding 4g of diatomite into the organic layer for decoloring, filtering out the diatomite, and then evaporating the solvent to dryness under reduced pressure to obtain a crude product; the crude product obtained is subjected to column chromatography and then recrystallized by petroleum ether to obtain 21g of white crystals with the yield of 50%.
The white crystals obtained in example 1 were examined and the results were as follows:
GC：99.9%；
m.p.：32.5℃；
MS：m/s（%）
422（25），274（23），148（100），87（67）；
1H-NMR：（ppm）
0.90（3H），1.28（m，8H），1.53（m，6H），1.75（m，4H），2.36（m，1H），2.49（m，2H），2.61（m，1H），6.89（m，2H）；
△：13.6（20℃，589nm）；
△n：0.064（20℃，1000Hz）；
the detection results prove that the obtained white crystal is
Example 2
Preparation of Compounds I-b:
the preparation of compounds I-b was carried out starting from the intermediates I-a-4 prepared in example 1, according to the synthetic route:
the preparation method comprises the following specific steps:
2.1 preparation of intermediate I-a-4:
the intermediates I-a-4 were prepared according to the preparation methods of steps 1.1 to 1.4 in example 1.
2.2 reaction of I-b-1The preparation of (1):
the synthesis was performed according to the method in the literature peer.kirsch et al, angelw.chem.int.ed., 2001.40.1480.
2.3 preparation of Compounds I-b
Adding 29.2g (0.11 mol) of intermediate I-a-4, 38.9g (0.1mol) of reactant I-b-1, 0.3g of palladium tetratriphenylphosphine, 15g of sodium carbonate, 100ml of toluene, 100ml of water and 100ml of ethanol into a reaction bottle, heating to reflux under stirring, and carrying out reflux reaction for 4 hours; cooling after the reaction is finished, adding 100ml of water for separating liquid, removing a water layer, and evaporating an organic layer to dryness to obtain a crude product;
the crude product is subjected to column chromatography and then recrystallized to obtain 37g of a final product with the yield of 70%.
The white crystals obtained in example 2 were used for detection, and the detection results were as follows:
GC：99.9%；
m.p.：68℃；
MS：m/s（%）
528（2.8），381（100），283（21.3），265（6.5）；
1H-NMR：（ppm）
0.90（t，3H），1.29（m，4H），1.54（m，1H），1.78（m，3H），2.12（m，1H），2.36（m，1H），2.61（m，1H），3.80（t，1H），6.89（m，2H），7.22（d，2H），7.38（m，4H）；
△：22.3（20℃，589nm）；
△n：0.129（20℃，1000Hz）；
c.p.：85℃。
the detection results prove that the obtained white crystal is
Example 3
Preparation of Compounds I-c:
the preparation of compounds I-c was carried out starting from the intermediate I-a-2 prepared in example 1, according to the synthetic route:
the preparation method comprises the following specific steps:
3.1 preparation of intermediate I-a-2:
the intermediate I-a-2 was prepared according to the preparation method of step 1.1 to step 1.2 in example 1.
3.2 preparation of intermediate I-c-1:
adding 17.5g (0.1mol) of 3-fluorobromobenzene and 250ml of tetrahydrofuran into a reaction bottle, stirring and dissolving, cooling to-60 to-50 ℃, and dropwise adding 40ml of 2.5M (0.1mol) of butyllithium under the condition that the system temperature is not higher than-50 ℃; then, 15.8g (0.1mol) of tetrahydrofuran solution of the intermediate I-a-2 is continuously dripped (15.8 g of the intermediate I-a-2 is dissolved in 50ml of tetrahydrofuran), and the mixture is stirred and reacted for 30min after dripping; naturally heating to-20 ℃, adding 50ml of water for separating, discarding a water layer, washing an organic layer with 50ml of multiplied by 4 water, and evaporating the solvent to obtain a crude product;
dissolving the crude product in 40ml of dichloromethane, and cooling to-85 to-75 ℃; controlling the temperature to be not higher than-70 ℃, firstly adding 40ml of triethylsilane, then dropwise adding 40ml of boron trifluoride ethyl ether solution, and stirring and reacting for 1h after dropwise adding; after the reaction is finished, heating to-10 ℃, adding a saturated sodium bicarbonate solution for hydrolysis, standing for liquid separation, removing a water layer, and evaporating the solvent in an organic layer to dryness to obtain a final product 19g, namely an intermediate I-c-1; the yield thereof was found to be 80%.
3.3 preparation of intermediate I-c-2
Adding 23.8g (0.1mol) of intermediate I-c-2, 11.2g (0.1mol) of potassium tert-butoxide and 250ml of tetrahydrofuran into a reaction bottle, stirring and dissolving, and cooling to-70 to-60 ℃; dropping 13.5g (0.13mol) tetrahydrofuran solution of trimethyl borate (13.5 g trimethyl borate is dissolved in 50ml tetrahydrofuran) while stirring, controlling the temperature to be minus 60 plus or minus 5 ℃ and stirring for reaction for 30 min; after the reaction is finished, naturally heating to-20 ℃, adding 50ml of water and 10ml of concentrated hydrochloric acid, stirring for 30min, separating liquid, removing a water layer, washing an organic layer with 50ml of water multiplied by 4, and evaporating the solvent to obtain a final product 14.2g, namely an intermediate I-c-2; the yield is 50%; HPLC: 97 percent.
3.4 preparation of Compounds I-c
31.2g (0.11 mol) of intermediate I-c-2, 38.9g (0.1mol) of reactant I-b-1 (prepared according to step 2.2 in example 2), 0.3g of tetrakistriphenylphosphine palladium, 15g of sodium carbonate, 100ml of toluene, 100ml of water and 100ml of ethanol were charged into a reaction flask, and the mixture was heated to reflux with stirring and reacted for 4 hours under reflux; cooling after the reaction is finished, adding 100ml of water for separating liquid, removing a water layer, and evaporating an organic layer to dryness to obtain a crude product;
the crude product is subjected to column chromatography and then recrystallization to obtain 38.2g of a final product with the yield of 70%.
The white crystals obtained in example 3 were used for the detection, and the detection results were as follows:
GC：99.9%；
m.p.：65℃；
MS：m/s（%）
546（3.6），399（100），301（15.7），283（8.5）；
1H-NMR：（ppm）
0.90（t，3H），1.29（m，4H），1.54（m，1H），1.78（m，3H），2.12（m，1H），2.36（m，1H），2.61（m，1H），3.80（t，1H），6.89（m，3H），7.12（d，1H）7.22（d，2H）7.72（t，1H）；
△：22.3（20℃，589nm）；
△n：0.129（20℃，1000Hz）；
c.p.：75℃。
the detection results prove that the obtained substance is
As can be seen from the above examples 1 to 3, the liquid crystal compound containing a thiotetrahydropyranyl group and having the structure of the general formula I provided by the present invention has a wide nematic temperature range and a large dielectric anisotropy, and is very suitable for use as a liquid crystal monomer for liquid crystal display. Examples 1-3 above only provide methods for synthesizing three liquid crystal compounds having the structure of formula I, and other liquid crystal compounds of formula I can be synthesized according to the above synthetic route.
On the basis of the preparation processes of the above examples 1 to 3, the quality of the prepared liquid crystal compound is not affected by enlarging or reducing the reactant dosage in the same ratio.
In the following examples 4 to 11, liquid crystal compounds represented by general formulae I, II, III, and IV were weighed in proportion, respectively, and mixed to prepare liquid crystal compositions. The liquid crystal compounds represented by the general formulae II, III and IV to be used can be synthesized by a known method or can be obtained commercially. The liquid crystal composition is prepared by a conventional method, for example, by dissolving liquid crystal monomers of various components in a solvent at a high temperature, mixing, and then evaporating the solvent under a reduced pressure to obtain a liquid crystal composition; or mixing the liquid crystal monomers in proportion by adopting methods such as heating, ultrasonic wave, suspension and the like. Then, the obtained liquid crystal composition was filled between two substrates of a liquid crystal display to perform a performance test.
Example 4
The components and the formulation thereof in the liquid crystal composition are shown in table 1:
TABLE 1 component ratios of the liquid crystal composition of example 4
The liquid crystal composition of example 4 was subjected to a performance test, and the test results were: Δ n: 0.105; and (delta): 7.2; γ 1: 65; c.p: at 87 deg.C.
Example 5
The components and the formulation thereof in the liquid crystal composition are shown in table 2:
TABLE 2 component ratios of the liquid crystal composition of example 5
The liquid crystal composition of example 5 was subjected to a performance test, and the test results were: Δ n: 0.125; and (delta): 7.8 of; γ 1: 65; c.p: at 94 ℃.
Example 6
The components and the formulation thereof in the liquid crystal composition are shown in table 3:
table 3 component ratios of liquid crystal compositions of example 6
The liquid crystal composition of example 6 was subjected to a performance test, and the test results were: Δ n: 0.105; and (delta): 7.2; γ 1: 65; c.p: at 87 deg.C.
Example 7
The components and the formulation thereof in the liquid crystal composition are shown in table 4:
TABLE 4 component ratios of the liquid crystal composition of example 7
The liquid crystal composition of example 7 was subjected to a performance test, and the test results were: Δ n: 0.112; and (delta): 7.7; γ 1: 65; c.p: at 87 deg.C.
Example 8
The components and their formulation in the liquid crystal composition are shown in table 5 below:
TABLE 5 component ratios of the liquid crystal composition of example 8
The liquid crystal composition of example 8 was subjected to a performance test, and the test results were: Δ n: 0.110; and (delta): 6.9; γ 1: 63; c.p: at 87 deg.C.
Example 9
The components and their formulations in the liquid crystal composition are shown in table 6 below:
TABLE 6 component ratios of liquid crystal compositions of example 9
The liquid crystal composition of example 9 was subjected to a performance test, and the test results were: Δ n: 0.105; and (delta): 7.1; γ 1: 65; c.p: 85 ℃.
Example 10
The components of the liquid crystal composition and their formulations are shown in table 7 below:
TABLE 7 component ratios of the liquid crystal composition of example 10
The liquid crystal composition of example 10 was subjected to a performance test, and the test results were: Δ n: 0.111; and (delta): 7.5; γ 1: 68; c.p: at 90 ℃.
Example 11
The components and their formulations in the liquid crystal composition are shown in table 8 below:
TABLE 8 component ratios of liquid crystal compositions of example 11
The liquid crystal composition of example 11 was subjected to a performance test, and the test results were: Δ n: 0.120 of; and (delta): 7.3; γ 1: 62, a first step of mixing; c.p: 92 deg.C.
As can be seen from the performance parameters of the liquid crystal compositions shown in examples 4 to 11, the liquid crystal composition provided by the invention has high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and is suitable for manufacturing liquid crystal displays, especially TFT-LCD liquid crystal displays.
Although the present invention only exemplifies the specific compounds and the blending amounts (weight percentage) of the above 8 embodiments, and performs the performance test, the liquid crystal composition of the present invention can be further expanded and modified by using the liquid crystal compounds represented by the general formulas i, ii, iii, and iv according to the present invention on the basis of the above embodiments, and the object of the present invention can be achieved by properly adjusting the blending amounts.
Claims (6)
1. A liquid crystal compound containing a thiotetrahydropyranyl group, characterized in that: the liquid crystal compound is any one of compounds shown in formulas I-1 to I-7,
in the formula,
R1is-H or a linear alkyl group having 1 to 10 carbon atoms;
R2is-F, -Cl, -OCF3、-CF3、-CN、-NCS、-OCHF2Any one of the groups in (1);
L1、L2、L3、L4、L5、L6、L7、L8is-H or-F, respectively.
2. The liquid crystal compound containing a thiotetrahydropyranyl group according to claim 1, wherein: in the liquid crystal compounds shown in the formulas I-1 to I-7,
R1is-H or a linear alkyl group having 1 to 6 carbon atoms;
R2is-Cl, -F, -OCF3、-CF3Any one of the groups of-CN, -NCS.
3. The method for producing a liquid crystal compound containing a thiotetrahydropyranyl group according to any one of claims 1 or 2, characterized in that: the reaction route is as follows:
when preparing compounds of formula I-1, formula I-2, formula I-3, scheme A is used:
the specific conditions of the reactions in the steps of the route A are respectively as follows:
preparation of intermediate b:
putting reaction raw materials a, reactants of methyl acrylate, trimethylsilyl diethylamine, p-hydroxyanisole and solvent of acetonitrile into a reactor, and carrying out reflux reaction under the protection of nitrogen; after the reaction is finished, evaporating the solvent, adding glacial acetic acid and water, and continuing to perform reflux reaction; cooling after the reaction is finished, and adding methyl tert-butyl ether for extraction and liquid separation; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
adding a solvent methanol into the evaporated material, and adding sodium borohydride at the controlled temperature of 0-10 ℃ to perform reduction reaction; after the reaction is finished, adding water and methyl tert-butyl ether for extraction and liquid separation, and evaporating the solvent in the organic layer to dryness to obtain a secondary evaporated material;
adding catalyst p-toluenesulfonic acid and solvent toluene into the secondary evaporated material, and carrying out reflux reaction; after the reaction is finished, adding water and toluene for extraction and liquid separation, evaporating the solvent in the organic layer to dryness to obtain an intermediate b crude product, and refining to obtain an intermediate b;
preparation of intermediate c:
putting the intermediate b, a reactant trimethyl silicon iodide and a solvent dichloromethane into a reactor, and reacting at 25 +/-5 ℃; adding water after the reaction is finished, and separating liquid; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
adding reactant oxalyl chloride and solvent benzene into the steamed dry matter, and stirring for reaction at 25 +/-5 ℃; after the reaction is finished, evaporating the solvent, adding dichloromethane and triethylamine, and then introducing hydrogen sulfide gas into the reaction solution for reaction; adding a sodium bicarbonate solution after the reaction is finished, and separating liquid; evaporating the solvent in the organic layer to dryness to obtain an intermediate c;
preparation of intermediate d:
controlling the temperature to be minus 50 +/-5 ℃, dripping reactant butyl lithium into tetrahydrofuran solution containing 1, 4-dibromobenzene, continuously dripping the tetrahydrofuran solution of the intermediate c after dripping, and stirring for reaction; adding water for separating liquid after the reaction is finished; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
dissolving the evaporated material in dichloromethane, dripping reactants triethylsilane and boron trifluoride diethyl etherate at-75 +/-5 ℃, and keeping the temperature for reaction; after the reaction is finished, heating, adding a saturated sodium bicarbonate solution for hydrolysis, then extracting, separating liquid, and evaporating the solvent in the organic layer to dryness to obtain an intermediate d crude product; recrystallizing to obtain an intermediate d;
preparation of intermediate e:
controlling the temperature to be-75 +/-5 ℃, dropping reactant butyl lithium into the tetrahydrofuran solution containing the intermediate d, and continuing dropping the tetrahydrofuran solution of reactant trimethyl borate after dropping; after the dropwise addition is finished, heating to-20 +/-5 ℃, adding hydrochloric acid, stirring for reaction, and extracting and separating liquid after the reaction is finished; evaporating the solvent in the organic layer to dryness to obtain an intermediate e crude product, and recrystallizing to obtain an intermediate e;
preparation of intermediate f:
adding tetrahydrofuran, water and hydrogen peroxide into the intermediate e, and reacting at 40 +/-5 ℃; after the reaction is finished, adding water and dichloromethane for liquid separation, evaporating the solvent in the organic layer to dryness to obtain an intermediate f crude product, and recrystallizing to obtain an intermediate f;
preparation of intermediate g:
adding 5% palladium carbon and solvent toluene into the intermediate f, and carrying out catalytic hydrogenation reaction at 25 + -5 deg.C and 0.25 + -0.05 Mpa; after the reaction is finished, filtering out the catalyst, and evaporating the solvent to dryness to obtain an intermediate g;
preparation of intermediate h:
controlling the temperature to be-75 +/-5 ℃, dropping reactant butyl lithium into tetrahydrofuran solution containing reactant 2-trimethylsilyl-1, 3-dithiane, and slowly raising the temperature to 0 ℃ after dropping; then cooling to-75 +/-5 ℃ again, and dripping tetrahydrofuran solution containing the intermediate g; after the dropwise addition is finished, heating to-25 +/-5 ℃, and continuously stirring for reaction; after the reaction is finished, adding water for liquid separation, evaporating the solvent in the organic layer to dryness to obtain a crude product of an intermediate h, and recrystallizing to obtain the intermediate h;
preparation of final product I:
controlling the temperature to be minus 20 +/-5 ℃, dripping reactant trifluoromethanesulfonic acid into a dichloromethane solution containing the intermediate h, stirring for reaction for 30min, and continuously cooling to be minus 75 +/-5 ℃; under the condition of the temperature, firstly, a dichloromethane solution containing reactants 3,4, 5-trifluorophenol and triethylamine is dripped in, and then the reactant NEt is added rapidly33 HF; controlling the temperature to be-75 +/-5 ℃, dripping dichloromethane solution containing liquid bromine, and continuously stirring for reaction at the temperature; after the reaction is finished, heating to 0 +/-5 ℃, pouring the reaction liquid into an ice-water mixture, adjusting the pH value of the reactant system to 5-8 by using a sodium hydroxide solution, and then separating liquid; evaporating the solvent in the organic layer to dryness to obtain a crude product of a final product I, and performing column chromatography and recrystallization to obtain the final product I;
when L in the formulae I-4 and I-65、L6All are-H, L in formula I-5 or formula I-77、L8When all are-H, the process is carried out by route BSynthesizing:
the specific conditions of the reactions in the steps of the route B are respectively as follows:
preparation of intermediate b:
putting reaction raw materials a, reactants of methyl acrylate, trimethylsilyl diethylamine, p-hydroxyanisole and solvent of acetonitrile into a reactor, and carrying out reflux reaction under the protection of nitrogen; after the reaction is finished, evaporating the solvent, adding glacial acetic acid and water, and continuing to perform reflux reaction; cooling after the reaction is finished, and adding methyl tert-butyl ether for extraction and liquid separation; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
adding a solvent methanol into the evaporated material, and adding sodium borohydride at the controlled temperature of 0-10 ℃ to perform reduction reaction; after the reaction is finished, adding water and methyl tert-butyl ether for extraction and liquid separation, and evaporating the solvent in the organic layer to dryness to obtain a secondary evaporated material;
adding catalyst p-toluenesulfonic acid and solvent toluene into the secondary evaporated material, and carrying out reflux reaction; after the reaction is finished, adding water and toluene for extraction and liquid separation, evaporating the solvent in the organic layer to dryness to obtain an intermediate b crude product, and refining to obtain an intermediate b;
preparation of intermediate c:
putting the intermediate b, a reactant trimethyl silicon iodide and a solvent dichloromethane into a reactor, and reacting at 25 +/-5 ℃; adding water after the reaction is finished, and separating liquid; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
adding reactant oxalyl chloride and solvent benzene into the steamed dry matter, and stirring for reaction at 25 +/-5 ℃; after the reaction is finished, evaporating the solvent, adding dichloromethane and triethylamine, and then introducing hydrogen sulfide gas into the reaction solution for reaction; adding a sodium bicarbonate solution after the reaction is finished, and separating liquid; evaporating the solvent in the organic layer to dryness to obtain an intermediate c;
preparation of intermediate d:
controlling the temperature to be minus 50 +/-5 ℃, dripping reactant butyl lithium into tetrahydrofuran solution containing 1, 4-dibromobenzene, continuously dripping the tetrahydrofuran solution of the intermediate c after dripping, and stirring for reaction; adding water for separating liquid after the reaction is finished; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
dissolving the evaporated material in dichloromethane, dripping reactants triethylsilane and boron trifluoride diethyl etherate at-75 +/-5 ℃, and keeping the temperature for reaction; after the reaction is finished, heating, adding a saturated sodium bicarbonate solution for hydrolysis, then extracting, separating liquid, and evaporating the solvent in the organic layer to dryness to obtain an intermediate d crude product; recrystallizing to obtain an intermediate d;
preparation of intermediate e:
controlling the temperature to be-75 +/-5 ℃, dropping reactant butyl lithium into the tetrahydrofuran solution containing the intermediate d, and continuing dropping the tetrahydrofuran solution of reactant trimethyl borate after dropping; after the dropwise addition is finished, heating to-20 +/-5 ℃, adding hydrochloric acid, stirring for reaction, and extracting and separating liquid after the reaction is finished; evaporating the solvent in the organic layer to dryness to obtain an intermediate e crude product, and recrystallizing to obtain an intermediate e;
preparation of final product I:
adding reactants to intermediate eHeating up catalysts of palladium tetratriphenylphosphine, sodium carbonate, solvents of toluene, ethanol and water for reflux reaction; after the reaction is finished, adding water for separating liquid, and evaporating the solvent in the organic layer to dryness to obtain a crude product of a final product I; carrying out column chromatography and recrystallization to obtain a final product I;
when L in the formulae I-4 and I-65、L6At least one of the groups is-F, L in the formulae I-5 and I-77、L8When at least one is-F, the synthesis is carried out using scheme C:
the specific conditions of the reactions in the steps of the route C are respectively as follows:
preparation of intermediate b:
putting reaction raw materials a, reactants of methyl acrylate, trimethylsilyl diethylamine, p-hydroxyanisole and solvent of acetonitrile into a reactor, and carrying out reflux reaction under the protection of nitrogen; after the reaction is finished, evaporating the solvent, adding glacial acetic acid and water, and continuing to perform reflux reaction; cooling after the reaction is finished, and adding methyl tert-butyl ether for extraction and liquid separation; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
adding a solvent methanol into the evaporated material, and adding sodium borohydride at the controlled temperature of 0-10 ℃ to perform reduction reaction; after the reaction is finished, adding water and methyl tert-butyl ether for extraction and liquid separation, and evaporating the solvent in the organic layer to dryness to obtain a secondary evaporated material;
adding catalyst p-toluenesulfonic acid and solvent toluene into the secondary evaporated material, and carrying out reflux reaction; after the reaction is finished, adding water and toluene for extraction and liquid separation, evaporating the solvent in the organic layer to dryness to obtain an intermediate b crude product, and refining to obtain an intermediate b;
preparation of intermediate c:
putting the intermediate b, a reactant trimethyl silicon iodide and a solvent dichloromethane into a reactor, and reacting at 25 +/-5 ℃; adding water after the reaction is finished, and separating liquid; evaporating the solvent in the organic layer to dryness to obtain an evaporated substance;
adding reactant oxalyl chloride and solvent benzene into the steamed dry matter, and stirring for reaction at 25 +/-5 ℃; after the reaction is finished, evaporating the solvent, adding dichloromethane and triethylamine, and then introducing hydrogen sulfide gas into the reaction solution for reaction; adding a sodium bicarbonate solution after the reaction is finished, and separating liquid; evaporating the solvent in the organic layer to dryness to obtain an intermediate c;
preparation of intermediate d':
controlling the temperature to be minus 50 +/-5 ℃, dripping reactant butyl lithium into tetrahydrofuran solution containing 3-bromofluorobenzene, continuously dripping the tetrahydrofuran solution of the intermediate c after dripping, and stirring for reaction; adding water for separating liquid after the reaction is finished, and evaporating the solvent in the organic layer to dryness to obtain a dried substance;
dissolving the evaporated material in dichloromethane, dripping reactants triethylsilane and boron trifluoride diethyl etherate at-75 +/-5 ℃, and reacting at the temperature; after the reaction is finished, heating, adding saturated sodium bicarbonate solution for hydrolysis, separating liquid, and evaporating the solvent in the organic layer to dryness to obtain an intermediate d';
preparation of intermediate e':
controlling the temperature to be minus 95 +/-5 ℃, dropping reactant butyl lithium into tetrahydrofuran solution containing intermediate d' and potassium tert-butoxide, and continuing dropping the tetrahydrofuran solution of reactant trimethyl borate after dropping; after the dropwise addition is finished, heating to-20 +/-5 ℃, adding hydrochloric acid and water, and stirring for reaction for 30 min; after the reaction is finished, separating liquid, and evaporating the solvent in the organic layer to dryness to obtain an intermediate e';
preparation of final product I:
addition of reactants to intermediate eHeating up catalysts of palladium tetratriphenylphosphine, sodium carbonate, solvents of toluene, ethanol and water for reflux reaction; after the reaction is finished, adding water for separating liquid, and evaporating the solvent in the organic layer to dryness to obtain a crude product of a final product I; and (4) carrying out column chromatography and recrystallization to obtain a final product I.
4. A liquid crystal composition characterized by: the liquid crystal composition comprises at least one liquid crystal compound shown as a general formula I in any one of claims 1-2; the weight percentage of the liquid crystal compound shown in the general formula I in the liquid crystal composition is less than or equal to 40% and is not zero.
5. A liquid crystal composition according to claim 4, wherein: the liquid crystal composition also comprises 4 to 50 weight percent of compound shown in a general formula II, 5 to 50 weight percent of compound shown in a general formula III and 3 to 45 weight percent of compound shown in a general formula IV,
wherein,
R3、R4、R5、R6、R7respectively is any one of-CN, -F, alkyl with 1 to 7 carbon atoms, alkoxy with 1 to 7 carbon atoms, alkenyl with 2 to 7 carbon atoms or fluoro alkoxy with 1 to 5 carbon atoms;
Z3、Z4are each a single bond, -CH2CH2-、-CH＝CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2Any one of (1) to (1);
each is a single bond or any of the following groups:
is any one of the following groups:
Y1、Y2are-H or-F, respectively;
n5、n6each is 0, 1, or 2.
6. A liquid crystal composition according to claim 5, wherein: the liquid crystal composition comprises 8-19 wt% of a liquid crystal compound shown in a general formula I, 20-36 wt% of a liquid crystal compound shown in a general formula II, 31-47 wt% of a liquid crystal compound shown in a general formula III and 5-33 wt% of a liquid crystal compound shown in a general formula IV.
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