CN103664539A - Spiro [3,5] nonane derivative, and preparation method and application thereof - Google Patents
Spiro [3,5] nonane derivative, and preparation method and application thereof Download PDFInfo
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- CN103664539A CN103664539A CN201310625996.0A CN201310625996A CN103664539A CN 103664539 A CN103664539 A CN 103664539A CN 201310625996 A CN201310625996 A CN 201310625996A CN 103664539 A CN103664539 A CN 103664539A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- VMWOETMUNAQFAX-UHFFFAOYSA-N spiro[3.5]nonane Chemical class C1CCC21CCCCC2 VMWOETMUNAQFAX-UHFFFAOYSA-N 0.000 title abstract description 6
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 113
- 150000001875 compounds Chemical class 0.000 claims abstract description 82
- 239000000203 mixture Substances 0.000 claims abstract description 62
- 125000003545 alkoxy group Chemical group 0.000 claims description 44
- 125000003342 alkenyl group Chemical group 0.000 claims description 38
- 125000000217 alkyl group Chemical group 0.000 claims description 29
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 20
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000012769 display material Substances 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000011737 fluorine Substances 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 claims description 2
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 claims description 2
- 125000004428 fluoroalkoxy group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 2
- 150000003254 radicals Chemical class 0.000 claims description 2
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims 2
- LMBFAGIMSUYTBN-MPZNNTNKSA-N teixobactin Chemical compound C([C@H](C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H](CCC(N)=O)C(=O)N[C@H]([C@@H](C)CC)C(=O)N[C@@H]([C@@H](C)CC)C(=O)N[C@@H](CO)C(=O)N[C@H]1C(N[C@@H](C)C(=O)N[C@@H](C[C@@H]2NC(=N)NC2)C(=O)N[C@H](C(=O)O[C@H]1C)[C@@H](C)CC)=O)NC)C1=CC=CC=C1 LMBFAGIMSUYTBN-MPZNNTNKSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 6
- 239000002904 solvent Substances 0.000 description 71
- 239000000376 reactant Substances 0.000 description 60
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 54
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 32
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000000047 product Substances 0.000 description 30
- 238000006243 chemical reaction Methods 0.000 description 27
- 238000003756 stirring Methods 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 23
- 239000000243 solution Substances 0.000 description 22
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 238000003786 synthesis reaction Methods 0.000 description 16
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- 238000001704 evaporation Methods 0.000 description 11
- 238000004817 gas chromatography Methods 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 238000010992 reflux Methods 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- 230000000704 physical effect Effects 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 0 *C(C1)CC1(CC1)CCC1C1CCC(*)CC1 Chemical compound *C(C1)CC1(CC1)CCC1C1CCC(*)CC1 0.000 description 4
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 4
- RXWOHFUULDINMC-UHFFFAOYSA-N 2-(3-nitrothiophen-2-yl)acetic acid Chemical compound OC(=O)CC=1SC=CC=1[N+]([O-])=O RXWOHFUULDINMC-UHFFFAOYSA-N 0.000 description 4
- 239000007818 Grignard reagent Substances 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 238000012790 confirmation Methods 0.000 description 4
- FIGYBMDNOMRNFK-UHFFFAOYSA-N dithian-1-ium trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.[SH+]1SCCCC1 FIGYBMDNOMRNFK-UHFFFAOYSA-N 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 4
- PVFOMCVHYWHZJE-UHFFFAOYSA-N trichloroacetyl chloride Chemical compound ClC(=O)C(Cl)(Cl)Cl PVFOMCVHYWHZJE-UHFFFAOYSA-N 0.000 description 4
- AQRLNPVMDITEJU-UHFFFAOYSA-N triethylsilane Chemical compound CC[SiH](CC)CC AQRLNPVMDITEJU-UHFFFAOYSA-N 0.000 description 4
- ZRTWIJKGTUGZJY-UHFFFAOYSA-N 3,4,5-trifluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1 ZRTWIJKGTUGZJY-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000013213 extrapolation Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- HYDVVGSQURFARM-UHFFFAOYSA-N iodomethane;phosphane Chemical compound P.IC HYDVVGSQURFARM-UHFFFAOYSA-N 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- SHQSVMDWKBRBGB-UHFFFAOYSA-N cyclobutanone Chemical class O=C1CCC1 SHQSVMDWKBRBGB-UHFFFAOYSA-N 0.000 description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- QWQBQRYFWNIDOC-UHFFFAOYSA-N (3,5-difluorophenyl)boronic acid Chemical compound OB(O)C1=CC(F)=CC(F)=C1 QWQBQRYFWNIDOC-UHFFFAOYSA-N 0.000 description 1
- WLPATYNQCGVFFH-UHFFFAOYSA-N 2-phenylbenzonitrile Chemical compound N#CC1=CC=CC=C1C1=CC=CC=C1 WLPATYNQCGVFFH-UHFFFAOYSA-N 0.000 description 1
- DRLVMOAWNVOSPE-UHFFFAOYSA-N 2-phenylcyclohexan-1-one Chemical compound O=C1CCCCC1C1=CC=CC=C1 DRLVMOAWNVOSPE-UHFFFAOYSA-N 0.000 description 1
- VSNLJDIYVSNZBH-UHFFFAOYSA-N 3,5-difluorocyclohexan-1-one Chemical compound FC1CC(F)CC(=O)C1 VSNLJDIYVSNZBH-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 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
- 150000001335 aliphatic alkanes Chemical class 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
- 230000005540 biological transmission Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- OZNRMDOOJBSJBA-UHFFFAOYSA-N cyclobutanone;hydrochloride Chemical compound Cl.O=C1CCC1 OZNRMDOOJBSJBA-UHFFFAOYSA-N 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 1
- 239000002274 desiccant Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C43/00—Ethers; Compounds having groups, groups or groups
- C07C43/02—Ethers
- C07C43/20—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring
- C07C43/225—Ethers having an ether-oxygen atom bound to a carbon atom of a six-membered aromatic ring containing halogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/16—Preparation of ethers by reaction of esters of mineral or organic acids with hydroxy or O-metal groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
- C09K19/46—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing esters
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/50—Spiro compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mathematical Physics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Liquid Crystal Substances (AREA)
Abstract
The invention discloses a spiro [3,5] nonane derivative, and a preparation method and application thereof. The structural general formula of the compound is as shown in a formula I (refer to the Specification). The compound has a stable structure, wide liquid crystal state temperature range, high low-temperature intersolubility and large dielectric anisotropy delta epsilon, can realize low threshold voltage and low rotary viscosity gamma 1 when being used by an optical device, can improve the performance of a liquid crystal composite material and a display and has important significance in realizing quick response of the display. A liquid crystal composition containing the compound can be applied to preparation of a liquid crystal display with low driving voltage, wide temperature range and high response speed. The formula I is shown in specifications.
Description
Technical Field
The invention belongs to the field of synthesis and application of liquid crystal compounds, and relates to a spiro [3,5] nonane derivative, and a preparation method and application thereof.
Background
Liquid crystal displays using the liquid crystal composition are widely used in displays of instruments, computers, televisions, and the like. In the field of liquid crystal display technology, although the market is very large and the technology is mature in recent years, the demand of people for display technology is continuously increasing, especially in the aspects of realizing quick response, reducing driving voltage to reduce power consumption 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.
Liquid crystal display elements are classified into the following modes according to display modes: twisted Nematic (TN) mode, Super Twisted Nematic (STN) mode, in-plane mode (IPS), Vertical Alignment (VA) mode. The following properties are required for the liquid crystal composition regardless of the display mode:
(1) the chemical and physical properties are stable;
(2) the viscosity is low;
(3) with a suitable Δ ε;
(4) suitable refractive index Δ n;
(5) has good compatibility with other liquid crystal compounds.
Liquid crystal materials for display have been developed, and a large number of liquid crystal compounds have appeared. The liquid crystal compounds are developed from biphenyl nitrile, esters, oxygen-containing heterocycles and pyrimidine rings to cyclohexyl benzene, phenylacetylene, ethyl bridges, alkenyl-terminated liquid crystals, various fluorine-containing aromatic ring liquid crystal compounds and the like, and the display performance requirements of TN, STN, TFT-LCD and the like are continuously met.
Any liquid crystal composition for display is required to have a wide liquid crystal state temperature, high stability, a relatively suitable viscosity, and a relatively fast response speed to an electric field. However, to date, no single liquid crystal monomer has been used alone in liquid crystal displays without being combined with other compounds to meet performance requirements.
Disclosure of Invention
The invention aims to provide a spiro [3,5] nonane derivative and a preparation method and application thereof.
The invention provides a liquid crystal compound of spiro [3,5] nonane derivative, which is shown as a formula I,
formula I
In the formula I, R1And R2Are selected from any one of the groups a, b or c:
a. selected from H, Cl, F, -CN, -OCN, -OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-SCN、-NCS、-SF5At least one of an alkyl group having 1 to 15 carbon atoms in total, an alkoxy group having 1 to 15 carbon atoms in total, an alkenyl group having 2 to 15 carbon atoms in total, and an alkenyloxy group having 2 to 15 carbon atoms in total;
b. containing-CH2One or at least two of said groups a of-are not adjacent-CH2-a group substituted with at least one of the following groups without direct connection of oxygen atoms: -CH = CH-, -C ≡ C-, -COO-, -OOC-, cyclobutane, -O-, and-S-;
c. a group obtained by substituting at least one hydrogen of the groups a or b with fluorine or chlorine;
Z1and Z2Are all single bonds, -CH2-、-CH2-CH2-、-（CH2）3-、-(CH2)4-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-or-CF ═ CF —;
a. b, c and d are integers of 0-3, and a + b + c + d is less than or equal to 5;
when a or b or c or d is 2 or 3,A1、A2-Z1、A3and A4-Z2The radicals indicated are all identical or different.
In the formula I, the C-C alkyl is specifically selected from at least one of C-C alkyl, C-C alkyl and C-C alkyl;
the alkoxy of C1-C15 is selected from C2-C15, C3-C15, C4-C15, C5-C15, C6-C15, C1-C6, C2-C6, C3-C6, C4-C6, C5-C6, C1-C5 and C2-C5, at least one of alkoxy of C3-C5, alkoxy of C4-C5, alkoxy of C1-C4, alkoxy of C2-C4, alkoxy of C3-C4, alkoxy of C1-C3, alkoxy of C1-C10, alkoxy of C2-C10, alkoxy of C3-C10, alkoxy of C1-C10, alkoxy of C1-C2 and alkoxy of C2-C3;
the alkenyl group of C2-C15 is specifically selected from at least one of an alkenyl group of C3-C15, an alkenyl group of C4-C15, an alkenyl group of C5-C15, an alkenyl group of C6-C15, an alkenyl group of C1-C6, an alkenyl group of C2-C6, an alkenyl group of C3-C6, an alkenyl group of C4-C6, an alkenyl group of C5-C6, an alkenyl group of C2-C5, an alkenyl group of C3-C5, an alkenyl group of C4-C5, an alkenyl group of C2-C4, an alkenyl group of C3-C4, an alkenyl group of C2-C10, an alkenyl group of C3-C10, an alkenyl group of C2-C8 and an alkenyl group of C2-C3;
the alkenyloxy of C2-C15 is specifically selected from at least one of alkenyloxy of C3-C15, alkenyloxy of C4-C15, alkenyloxy of C5-C15, alkenyloxy of C6-C15, alkenyloxy of C2-C6, alkenyloxy of C3-C6, alkenyloxy of C4-C6, alkenyloxy of C5-C6, alkenyloxy of C2-C5, alkenyloxy of C3-C5, alkenyloxy of C4-C5, alkenyloxy of C2-C4, alkenyloxy of C3-C4, alkenyloxy of C2-C10, alkenyloxy of C3-C10, alkenyloxy of C2-C8 and alkenyloxy of C2-C3;
the compound shown in the formula I is any one of compounds shown in formulas I-1 to I-4:
wherein the compound shown in the formula I-1 is specifically any one of the following compounds:
the compound shown in the formula I-7 is specifically a compound shown in a formula I-15:
the compound shown in the formula I-2 is specifically any one of the following compounds:
the compound shown in the formula I-3 is specifically any one of the following compounds:
the compound shown in the formula I-4 is specifically any one of the following compounds:
the compound shown in the formula I-10 is specifically a compound shown in a formula I-14 or a formula I-16:
the compound shown in the formula I-12 is specifically a compound shown in a formula I-17:
in the formulae I-1 to I-13, R1、R2、
Are as defined in formula I above;
L1to L8Are both selected from any one of hydrogen and fluorine.
The preparation of the compound of formula I above is as follows:
when in use
Is composed ofThe method comprises the following steps:
the method specifically comprises the following steps: will be provided withAnhydrous potassium carbonate,Reacting for 2 hours at 65-70 ℃;
wherein,anhydrous potassium carbonate andthe feeding molar ratio of (1): 2: 1.2;
wherein, the reactants
Can be prepared according to various conventional methods: the preparation method can be prepared according to the following steps:
1) mixing 1mol of iodomethane phosphonium salt and 1mol of potassium tert-butoxide at 0 ℃ and then 0.8mol
After 1 hour of reaction, the product
2) Subjecting the product obtained in step 1)
The catalyst zinc powder I, copper (II) acetate monohydrate and trichloroacetyl chloride react in ether for 24 hours, and the obtained product reacts with the zinc powder II at the temperature of 80 ℃ for 2 hours to obtain
Wherein,the dosage ratio of the catalyst zinc powder I, the copper (II) acetate monohydrate, the trichloroacetyl chloride and the zinc powder II is 0.3 mol: 0.483 mol: 1.5 g: 0.33 mol: 36.5 g;
3) refluxing magnesium chips and bromopropane in tetrahydrofuran to react to obtain a Grignard reagent, cooling to 20 ℃, and adding the Grignard reagent obtained in the step 2)
Reacting the tetrahydrofuran solution for 2 hours, and reacting the obtained product with triethylsilylhydride and boron trifluoride diethyl etherate for 2 hours at the temperature of between 25 and 20 ℃ below zero under the protection of nitrogen to obtain
Wherein, the magnesium chips, the bromopropane,
The ratio of the amount of triethylsilylhydride to boron trifluoride etherate was 6.6 g: 30.8 g: 0.2 mol: 0.397 mol: 0.397 mol;
4) subjecting the product obtained in step 3)
Reacting with n-butyl lithium at-55 to-60 ℃ for 1 hour in nitrogen atmosphere, then adding difluorodibromomethane to react for 30 minutes at-65 to-70 ℃ to obtain
Wherein,n-butyllithium and difluorodibromomethaneThe feeding molar ratio of the alkane is 1: 1.1: 1.3;
when in use
In the case of phenyl or cyclohexyl, the following procedure is followed:
the method specifically comprises the following steps:
will be provided withAnd triethylamine at-70 ℃ with
After 1 hour of reaction, NEt was added33HF and liquid bromine react for 1 hour and then are heated to 0 ℃ to obtain;
wherein,
triethylamine,
NEt33 the ratio of the amounts of HF and liquid bromine is 1: 1: 1: 4: 4;
wherein, the reactants
Can be prepared according to various conventional methods; the preparation method can be prepared according to the following steps:
the first and second methods are both carried out in an organic solvent; the organic solvent can be at least one of tetrahydrofuran, diethyl ether, ethanol, toluene and dichloromethane which are commonly used;
the invention also provides a liquid crystal mixture which comprises the compound shown in the formula I.
The liquid-crystal mixtures described above may also consist exclusively of compounds of the formulae I and II to IV:
In the formulae II to IV, R1、R2And R3At least one selected from the group consisting of a hydrogen atom, a halogen, -CN, an alkyl group having 1 to 7 carbon atoms in total, an alkoxy group having 1 to 7 carbon atoms in total, an alkenyl group having 2 to 7 carbon atoms in total, and a fluoroalkoxy group having 1 to 5 carbon atoms in total;
z is selected from single bond, -CH2-CH2-、-CH=CH-、-C≡C-、-COO-、-OOC-、-OCH2-、-CH2O-、-CF2O-and-OCF2-at least one of;
Y1and Y2Both selected from at least one of H and F;
p is an integer of 0 to 2;
when the P is 2, the compound is,
the same or different.
In the formulas II to IV, the alkyl of C1-C7 is specifically selected from at least one of alkyl of C2-C7, alkyl of C3-C7, alkyl of C4-C7, alkyl of C5-C7, alkyl of C6-C7, alkyl of C1-C6, alkyl of C2-C6, alkyl of C3-C6, alkyl of C4-C6, alkyl of C5-C6, alkyl of C1-C5, alkyl of C2-C5, alkyl of C3-C5, alkyl of C4-C5, alkyl of C1-C4, alkyl of C2-C4, alkyl of C3-C4, alkyl of C1-C3, alkyl of C1-C2 and alkyl of C2-C3 8;
the alkoxy group of C1-C7 is specifically selected from at least one of alkoxy groups of C2-C7, alkoxy groups of C3-C7, alkoxy groups of C4-C7, alkoxy groups of C5-C7, alkoxy groups of C6-C7, alkoxy groups of C1-C6, alkoxy groups of C2-C6, alkoxy groups of C3-C6, alkoxy groups of C4-C6, alkoxy groups of C5-C6, alkoxy groups of C1-C5, alkoxy groups of C2-C5, alkoxy groups of C3-C5, alkoxy groups of C4-C5, alkoxy groups of C1-C4, alkoxy groups of C2-C4, alkoxy groups of C3-C4, alkoxy groups of C1-C3, alkoxy groups of C1-C2 and alkoxy groups of C2-C3;
the alkenyl of C2-C7 is specifically selected from at least one of alkenyl of C3-C7, alkenyl of C4-C7, alkenyl of C5-C7, alkenyl of C6-C7, alkenyl of C2-C6, alkenyl of C3-C6, alkenyl of C4-C6, alkenyl of C5-C6, alkenyl of C2-C5, alkenyl of C3-C5, alkenyl of C4-C5, alkenyl of C2-C4, alkenyl of C3-C4 and alkenyl of C2-C3;
the fluorinated alkoxy of C2-C5 is specifically selected from at least one of fluorinated alkoxy of C3-C5, fluorinated alkoxy of C4-C5, fluorinated alkoxy of C2-C4, fluorinated alkoxy of C3-C4 and fluorinated alkoxy of C2-C3;
in the liquid crystal mixture, the mass ratio of the compounds shown in the formulas I to IV is 0-40: 4-50: 5-50: 3-45, and the mass of the compound shown in the formula I is not 0.
The mass ratio of the compounds shown in the formulas I to IV is specifically 24: 32: 35: 9. 4: 24: 35: 37. 12: 36: 36: 16. 15: 30: 31: 24. 12: 18: 38: 32. 4-24: 24-32: 35: 9-37, 12-15: 16-32: 31-38: 18-36, 15-24: 9-24: 31-35: 30-32;
specifically, the liquid crystal mixture is specifically the following liquid crystal mixtures a, b, c, d or e:
the liquid crystal mixture a comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture a specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture b comprises or consists of the following components in parts by mass:
the liquid crystal mixture b specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture c comprises or consists of the following components in parts by mass:
the liquid crystal mixture c specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture d comprises or consists of the following components in parts by mass:
the liquid crystal mixture d specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture e comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture e specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
in addition, the application of the compound shown in the formula I and the liquid crystal mixture provided by the invention in preparing a liquid crystal display material, an electro-optical display material or an electro-optical liquid crystal display, and the liquid crystal display material, the electro-optical display material or the electro-optical liquid crystal display containing at least one of the liquid crystal compound shown in the formula I or the liquid crystal mixture belong to the protection scope of the invention. The electro-optical liquid crystal display is a TN type display, a VA type display, an IPS type display or a PDLC type display.
The compound shown in the formula I has general physical properties required by the compound, has photo-thermal stability, wide liquid crystal state temperature range, better low-temperature intersolubility and larger dielectric anisotropy Delta epsilon, and can realize lower threshold voltage and low rotational viscosity gamma when an optical device is used1The liquid crystal composition material and the display performance can be improved, and the method has important significance for realizing the quick response of the display. The liquid crystal composition containing the compound can be applied to preparing a liquid crystal display with low driving voltage, wide temperature range and high response speed.
Detailed Description
The present invention will be further illustrated with reference to the following specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The following examples are provided to illustrate the present invention, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The materials are commercially available from the open literature unless otherwise specified. In the following examples, GC means gas chromatography purity, HPLC means liquid chromatography purity, MP means melting point, MS means mass spectrum, 1H-NMR means nuclear magnetic hydrogen spectrum, DELTA epsilon means dielectric anisotropy, and DELTA n means optical anisotropy.
The structural correctness of the product shown in the formula I obtained in the following examples is confirmed by utilizing a mass spectrum chart obtained by gas chromatography, liquid chromatography, GC-MS and 1H-NMR identification. GC was measured by an Agilent HP6820 gas chromatograph, the GC-MS analyzer was an Agilent MS5975C, 1H-NMR was measured by a Bruker Biospin DRX-500 analyzer, and the melting point was measured by a WRX-1S micro-thermal analyzer with a temperature rise rate of 3 ℃/min.
The physical properties of the product of formula I obtained in the following examples were determined in two ways: the compound itself was measured as a sample and the compound was mixed with a mother liquid crystal to be measured as a sample. The physical properties of the compound were measured by mixing the compound with a mother liquid crystal as a sample: a sample was prepared by mixing 15% of a liquid crystal compound and 85% of a mother liquid crystal, and an extrapolated value was calculated from a measured value of the sample by an extrapolation method shown in the following formula,
the physical properties of the monomeric liquid-crystal compound were obtained by extrapolating the value = [100 × (measured value of sample) - (weight percentage of mother liquid crystal) × (measured value of mother liquid crystal) ]/weight percentage of the compound.
The matrix liquid crystal used had the following composition:
the method for measuring physical properties of liquid crystal compounds is carried out according to the specifications of the industry, see "handbook of liquid crystal devices" published by the publishers of the aviation industry
Method for measuring physical properties of compound:
1. determination of phase Structure and Transmission temperature (. degree. C.)
First, a compound was placed on a hot plate equipped with a polarizing microscope melting point meter model FP-52 (Mettler) company, and the phase type was determined by observing the phase change with a polarizing microscope while heating at a rate of 3 ℃/min.
② the transition temperature is determined by raising or lowering the temperature at a rate of 1 ℃/min by a differential calorimeter DSC822e of Mettler corporation and determining the starting point of the endothermic peak or the exothermic peak accompanying the phase change of the sample by extrapolation.
The crystal is represented by C, the smectic phase is S, the nematic phase is N, and the liquid is I.
2. Viscosity: eta. mpa.s at 20 ℃ using a volumetric viscometer. Gamma ray1Indicates rotational viscosity measured cP at 20 ℃ using a Toyo6254 comprehensive tester.
3. Optical anisotropy (refractive index anisotropy. DELTA.n measured at 25 ℃ C.), and the measurement of. DELTA.n was carried out at 25 ℃ C. with a light having a wavelength of 589nm using an Abbe refractometer. After rubbing the surface of the primary prism (Pri 3 m) in one direction, the sample was dropped onto the primary prism. Refractive index (n)11) The refractive index (n) is a value measured when the polarization direction is parallel to the rubbing direction⊥) Is a value measured when the polarization direction is perpendicular to the rubbing direction, and the value of optical anisotropy (Δ n) is represented by Δ n = n11-n⊥To calculate.
4. Dielectric anisotropy (. DELTA.. di-elect cons., measured at 25 ℃) was measured by precision LCR testing by Hewlett-packard HP4284aAnd (5) measuring by using the instrument. Measuring dielectric constant ε of liquid crystal molecules in long axis direction‖And the dielectric constant (. epsilon.) of the liquid crystal molecules in the minor axis direction was measured⊥) Dielectric anisotropy Δ ε by ∈ = ε‖-ε⊥To calculate.
Among the measured values, when the liquid crystal compound itself was used as a sample, the obtained value was recorded as an experimental value, and when a mixture of the liquid crystal compound and a mother liquid crystal was used as a sample, the value obtained by extrapolation was recorded as an experimental value.
Example 1 Compounds
Synthesis of (I-14) (method one)
Step 1 (I-14-a) Synthesis
Adding 101g (0.25 mol) of iodomethane phosphonium salt (reactant) into 400ml of tetrahydrofuran (solvent) in a 1L three-necked flask, cooling to 0 ℃ under stirring, adding 28g (0.25 mol) of potassium tert-butoxide (reactant) in batches, stirring for 1 hour after adding, dropwise adding 42g (0.2mol) of 3, 5-difluorocyclohexanone (reactant) and 100ml of tetrahydrofuran solution, stirring for 1 hour after dropwise adding, adding 300ml of water, stirring for 10 minutes, separating liquid, steaming out the solvent, adding 300ml of petroleum ether column chromatography, and steaming out the solvent to obtain 37.4g of a product with yield of 90 percent and gas chromatography purity of 97 percent;
synthesis of step 2 (I-14-b)
A1L three-necked flask was charged with 300ml of diethyl ether (solvent), 62.4g (0.3mol) (I-14-a) (reactant), 31.4g (0.483mol) of zinc (catalyst) and 1.5g of copper (II) acetate monohydrate (catalyst), followed by dropwise addition of 60g (0.33 mol) of trichloroacetyl chloride (reactant), and the reaction was allowed to proceed with exotherm to reflux and at room temperature for 24 hours. The solid was filtered off, discarded, the filtrate was washed with water, evaporated to dryness and purified by column chromatography to give 52.7g of cyclobutanone chloride as an oily substance.
Adding 200ml of glacial acetic acid (solvent) into the chlorinated cyclobutanone (reactant) obtained in the previous step, adding 36.5g of zinc powder (reactant) in batches at the temperature of less than 80 ℃, stirring for 2 hours at 80 ℃, cooling to room temperature, adding 200ml of water, adding 200ml of methyl tert-butyl ether, stirring for 10 minutes, separating, washing, drying, evaporating the solvent to dryness to obtain a product with the yield of 52.5g of 70% and the purity of 98% by gas chromatography;
synthesis of step 3 (I-14-c)
6.6g of magnesium chips (reactant) and 200ml of tetrahydrofuran (solvent) were added to a 1L three-necked flask, 30.8g of bromopropane (reactant) was added dropwise under heating and refluxing to prepare a Grignard reagent, and then the temperature was lowered to 20 ℃ to add 50g (0.2mol) of (I-14-b) (reactant) in tetrahydrofuran solution dropwise, followed by stirring for 2 hours, adding to 30ml of an aqueous hydrochloric acid solution, hydrolysis for 20 minutes, extraction with ethyl acetate, and spin-drying.
Adding the product obtained in the previous step into another 1L three-necked flask, 500ml of dry dichloromethane (solvent), cooling to-25-20 ℃ under the protection of nitrogen, dropwise adding 63.3ml (0.397 mol) of triethylsilylhydride (reactant), dropwise adding 50ml (0.397 mol) of boron trifluoride diethyl etherate (reactant) into the system, keeping the temperature at-25-20 ℃ after dropwise adding, stirring for 2 hours, naturally raising the temperature to 0 ℃, adding a saturated aqueous solution of sodium bicarbonate (adjusting the pH value) until no bubbles are released, separating, washing with water to be neutral, spin-drying the solvent, recrystallizing with 2 times of ethanol (solvent), and performing suction filtration to obtain nearly white crystal powder 38.9g, wherein the yield is 70%, and the purity of a gas chromatography is 99%.
Synthesis of step 4 (I-14-d)
27.8g (0.1 mol) (I-14-c) (reactant) and 200ml tetrahydrofuran (solvent) are added into a reaction bottle, nitrogen is introduced for protection, the temperature is reduced to minus 60 ℃, 0.11mol n-butyllithium (reactant) is dripped, the temperature is controlled between minus 55 ℃ and minus 60 ℃ in the dripping process, and the temperature is controlled and stirred continuously for reaction for 1 hour after dripping. Cooling to-70 ℃, dropwise adding a solution (reactant) of 28g (0.13 mol) of difluorodibromomethane and 100ml of tetrahydrofuran, controlling the temperature of-65 ℃ to-70 ℃ in the dropwise adding process, continuously stirring and reacting for 30 minutes at controlled temperature after dropwise adding, heating to room temperature, adding 20ml of concentrated hydrochloric acid (regulating the pH value) and 50ml of water (solvent) for hydrolysis, separating liquid, extracting an aqueous phase by 100ml of dichloromethane (solvent), washing an organic phase to neutrality by water, evaporating the solvent to dryness to obtain 40g (I-14-d) of light yellow liquid, wherein the yield is 90%, and the purity of a liquid chromatogram is 65%.
Step 5
0.1mol of (I-14-d) (reactant), 100ml of DMSO (solvent), 0.2mol of anhydrous potassium carbonate (reactant) and 0.12mol of 3,4, 5-trifluorophenol (reactant) are added into a reaction flask, stirred and heated to 65-70 ℃ for reaction for 2 hours. Cooling to room temperature, filtering the solid, washing the filter cake with 300ml dichloromethane (solvent), adding 100ml water into the filtrate, stirring, separating, extracting the water layer with 200ml dichloromethane (solvent), washing the organic phase to neutrality, and evaporating the solvent. Dissolving the concentrate in 500ml toluene (solvent), decolorizing with silica gel column, eluting with toluene (solvent), collecting eluate and evaporating to remove solvent, and recrystallizing the obtained product with anhydrous ethanol (solvent) for 3 times to obtain white needle crystal (I-14) with yield of 40% and gas chromatography purity of 99.9%.
The structure confirmation data for this product are as follows:
MP：60℃；
MS：m/s%474(3.2),327(100),176(2.8),189(3.7),
1H-NMR：δ（ppm）0.90(t,3H),1.28(m,4H),1.44(m,4H)1.65(m,4H),1.90(m,5H),2.72(，m，1H),6.54(d,2H),6.89(m,2H)；
as can be seen from the above, the product has a correct structure and is a compound represented by formula I-14.
The liquid crystal properties of the compound are shown below:
△ε：15.3（20℃，589nm）
△n：0.119（20℃，1000Hz）
from the aboveThe compound has photo-thermal stability, wide liquid crystal state temperature range, better low-temperature intersolubility and larger dielectric anisotropy Delta epsilon, and can realize lower threshold voltage and low rotational viscosity Gamma when an optical device is used1The liquid crystal composition material and the display performance can be improved, and the method has important significance for realizing the quick response of the display.
Examples 2,
Synthesis of (method one)
Step 1 (I-15-a) Synthesis
Adding 400ml tetrahydrofuran (solvent) 101g (0.25 mol) methyl iodide phosphine salt (reactant) into a 1L three-necked flask, cooling to 0 ℃ under stirring, adding 28g (0.25 mol) potassium tert-butoxide (reactant) in batches, stirring for 1 hour after adding, dropwise adding a solution of 34.8g (0.2mol) phenylcyclohexanone (reactant) and 100ml tetrahydrofuran, stirring for 1 hour after dropwise adding, adding 300ml water, stirring for 10 minutes, separating liquid, evaporating the solvent, adding 500ml petroleum ether column chromatography, evaporating the solvent to obtain 31g of a product, wherein the yield is 90%, and the purity of a gas chromatography is 97%
Synthesis of step 2 (I-15-b)
A1L three-necked flask was charged with 400ml of diethyl ether (solvent), 51.6g (0.3mol) (I-15-a) (reactant), 31.4g (0.483mol) of zinc (catalyst) and 1.5g of copper (II) acetate monohydrate (catalyst), followed by dropwise addition of 60g (0.33 mol) of trichloroacetyl chloride (reactant), and the reaction was allowed to proceed with exotherm to reflux and at room temperature for 24 hours. The solid was filtered off, discarded, the filtrate washed with water, evaporated to dryness and purified by column chromatography to give 80g of an oil.
Adding 200ml glacial acetic acid (solvent) into the chlorinated cyclobutanone (reactant) in the previous step, adding 36.5g zinc powder (reactant) in batches at the temperature of less than 80 ℃, stirring for 2 hours at 80 ℃, cooling to room temperature, adding 200ml water, adding 200ml methyl tert-butyl ether, stirring for 10 minutes, separating, washing, drying, evaporating the solvent to obtain 45g of product, wherein the yield is 70%, and the purity of a gas chromatography is 98%.
Synthesis of step 3 (I-15-c)
6.6g of magnesium chips (reactant) and 200ml of tetrahydrofuran (solvent) were added to a 1L three-necked flask, 30.8g of bromopropane (reactant) was added dropwise under heating and refluxing to prepare a Grignard reagent, and then, the temperature was lowered to 20 ℃ to add 42.8g (0.2mol) (I-15-b) (reactant) of tetrahydrofuran solution dropwise, followed by stirring for 2 hours, adding to 30ml of an aqueous hydrochloric acid solution, hydrolysis for 20 minutes, extraction with ethyl acetate, and spin-drying.
Adding the product obtained in the previous step into another 1L three-necked flask, 500ml of dry dichloromethane (solvent), cooling to-25-20 ℃ under the protection of nitrogen, dropwise adding 63.3ml (0.397 mol) of triethylsilylhydride (reactant), dropwise adding 50ml (0.397 mol) of boron trifluoride diethyl ether (reactant) into the system, stirring for 2 hours at-25-20 ℃ after dropwise adding, naturally raising to 0 ℃, adding a saturated aqueous solution of sodium bicarbonate (adjusting the pH value) until no bubbles are released, separating, washing with water to neutrality, spin-drying the solvent, distilling the product under reduced pressure to obtain 33.9g, obtaining the yield of 70%, and obtaining the purity of gas chromatography of 98%.
Synthesis of step 4 (I-15-d)
48.4g (0.2mol) (I-15-c) (reactant), 200ml dichloromethane (solvent), 10g anhydrous ferric chloride (catalyst) are added into a 1L three-necked bottle, 32g (0.2mol) liquid bromine (reactant) is added dropwise under the temperature controlled at 10 ℃, the reaction is stirred for 10 hours, 300ml water is added, and liquid separation and washing are carried out. Conventional treatment, recrystallizing the product with twice ethanol once to obtain 45g, yield 70%, and gas chromatography purity 98%
Synthesis of step 5 (I-15-e)
32.1g (0.1 mol) (I-15-d) (reactant), 15.8g (0.1 mol)3, 5-difluorophenylboronic acid (reactant), 0.3g tetratriphenylphosphine palladium (catalyst), 0.2mol potassium carbonate, 100ml toluene (solvent), 100ml ethanol (solvent) of water 100ml, heating and refluxing for 4 hours, cooling to room temperature, separating liquid, processing according to the conventional method, recrystallizing the product with two times ethanol once to obtain 28.3g product with purity of 98%
Synthesis of step 6 (I-15-f)
Adding 35.4g (0.1 mol) (I-15-e) (reactant) and 200ml tetrahydrofuran (solvent) into a reaction bottle, introducing nitrogen for protection, cooling to-60 ℃, dropwise adding 0.11mol n-butyllithium (reactant), controlling the temperature in the dropwise adding process to be-55 to-60 ℃, and continuing to control the temperature and stir for reaction for 1 hour after dropwise adding. Cooling to-70 ℃, dropwise adding a solution of 28g (0.13 mol) of difluorodibromomethane and 100ml of tetrahydrofuran, completing dropwise addition (reactant) within 2 hours, controlling the temperature of-65 ℃ to-70 ℃ in the dropwise adding process, continuing to control the temperature and stir for reaction for 30 minutes after the dropwise addition is completed, heating to room temperature, adding 20ml of concentrated hydrochloric acid (regulating the pH value) and 50ml of water (solvent) for hydrolysis, separating liquid, extracting the water phase by 100ml of dichloromethane (solvent), washing the organic phase with water to be neutral, evaporating the solvent to obtain 46g (I-15-f) of light yellow solid, wherein the purity yield is 61.7%, and the purity of the liquid chromatography is 65%.
Step 7
0.1mol (pure) (I-15-f) (reactant), 100ml DMSO (solvent), 0.2mol anhydrous potassium carbonate (reactant) and 0.12mol3, 4, 5-trifluorophenol (reactant) are added into a reaction bottle, stirred and heated to 65-70 ℃ for reaction for 2 hours. Cooling to room temperature, filtering the solid, washing the filter cake with 300ml dichloromethane (solvent), adding 100ml water into the filtrate, stirring, separating, extracting the water layer with 200ml dichloromethane (solvent), washing the organic phase to neutrality, and evaporating the solvent. Dissolving the concentrate in 500ml toluene (solvent), decolorizing with silica gel column, eluting with toluene (solvent), collecting eluate and evaporating to remove solvent, and recrystallizing the obtained product with anhydrous ethanol (solvent) for 3 times to obtain white needle crystal (I-15) with yield of 40% and gas chromatography purity of 99.9%.
The structure confirmation data for this product are as follows:
MP：85℃；
MS：m/s%：550（2.3），403(100),252(3.6),278(5.4)；
1H-NMR：δ（ppm）0.90(t,3H),1.2,9(m,4H),1.44(m,4H)1.67(m,4H),1.96(m,5H),2.72(，m，1H),6.89(m,2H),7.22(d,2H),7.36（s，4H）；
as can be seen from the above, the product has a correct structure and is a compound represented by the formula I-15.
The liquid crystal properties of the compound are shown below:
CP：120℃；
△ε：19.3（20℃，589nm）
△n：0.135（20℃，1000Hz）
from the above, the compound has photo-thermal stability, wide liquid crystal state temperature range, better low-temperature intersolubility and larger dielectric anisotropy Delta epsilon, and can realize lower threshold voltage and low rotational viscosity gamma when an optical device is used1The liquid crystal composition material and the display performance can be improved, and the method has important significance for realizing the quick response of the display.
Examples 3,
Synthesis of (method two)
Synthesis of step 1 (I-16-a)
Adding 0.1mol (I-15-d) (reactant) obtained in the step and 120ml tetrahydrofuran (solvent) into a reaction bottle, installing, sealing and stirring, introducing nitrogen to replace air, cooling to-70 ℃, dropwise adding 0.1mol butyl lithium (reactant) with the concentration of 2.5M, after the addition is finished for 20 minutes, introducing dry carbon dioxide gas (reactant) until saturation, after reacting at this temperature for 2 hours, the reaction solution was poured into a beaker containing 20ml of concentrated hydrochloric acid (pH adjustment) and 100ml of water for hydrolysis, separated, the aqueous phase was extracted once with 50ml of ethyl acetate (solvent), the organic phases were combined, washed with saturated brine to neutrality, dried over anhydrous sodium sulfate (desiccant), and concentrated to remove the solvent to obtain a pale yellow solid, which was recrystallized once with 2 times of toluene and 1 time of ethyl acetate (solvent) to obtain white crystals (I-16-a). The yield is 90%, and the liquid chromatography purity is 98.0%.
Step 2
Adding 0.1mol of (I-16-a), 30ml of toluene (solvent) and 30ml of isooctane (solvent) into a reaction bottle, adding 14g of 1, 3-propanedithiol (reactant), heating the suspension to 50 ℃ under stirring, adding 19.2g of trifluoromethanesulfonic acid (reactant) within 30 minutes, heating to reflux after the addition is finished, separating out the generated water, cooling to 50 ℃ after water is purified, adding 100ml of methyl tert-butyl ether (solvent), continuously cooling, precipitating crystals, filtering under the protection of nitrogen, washing the obtained crystals with methyl tert-butyl ether (solvent) (25 ml multiplied by 4), and drying in vacuum to obtain orange crystals (dithiane trifluoromethanesulfonate).
Step 3
A mixed solution of 0.1mol of 3,4, 5-trifluorophenol (reactant), 0.1mol of triethylamine (reactant) and 130ml of dichloromethane (solvent) was charged into a reaction flask and cooled to-70 ℃ and a solution of the above 0.1mol of the above-mentioned crystals (reactant) of dithiane trifluoromethanesulfonate in 120ml of dichloromethane (solvent) was added dropwise over 45 minutes, and after stirring at this temperature for one hour, 0.4mol of NEt was added within 5 minutes33HF (reactant). Then, 30ml of a dichloromethane (solvent) solution of 0.4mol of liquid bromine (reactant) was added at-70 ℃ for one hour, and the reaction was continued at-70 ℃ for one hour, and the temperature was raised to 0 ℃ to pour the reaction solution into 32% of a 160ml aqueous sodium hydroxide solution (pH adjustment) and 300g of ice, and the pH of the reaction solution was adjusted to 5 to 8 by dropwise addition of about 45g of 32% aqueous sodium hydroxide solution. Water phase after liquid separationExtraction with 80ml of dichloromethane (solvent) and the combined organic phases are filtered over 4g of kieselguhr (decolourant), washed with water and the solvent is evaporated off under reduced pressure. The crude product obtained was subjected to column chromatography and then recrystallized from petroleum ether (solvent) to obtain a white crystalline product (i-16) in a yield of 45%, GC: 99.8 percent.
The structure confirmation data for this product are as follows:
MP：50℃
MS：m/s%438（5.6），291(100),148(13.7),140(8.7),
1H-NMR：δ（ppm）0.90(t,3H),1.28(m,4H),1.44(m,4H)1.72(m,6H),1.97(m,3H),2.72(，m，1H),6.89(m,2H),7.25(m,4H)
as can be seen from the above, the product has a correct structure and is a compound represented by the formula I-16.
The liquid crystal properties of the compound are shown below:
△ε：12.3（20℃，589nm）
△n：0.115（20℃，1000Hz）
from the above, the compound has photo-thermal stability, wide liquid crystal state temperature range, better low-temperature intersolubility and larger dielectric anisotropy Delta epsilon, and can realize lower threshold voltage and low rotational viscosity gamma when an optical device is used1The liquid crystal composition material and the display performance can be improved, and the method has important significance for realizing the quick response of the display.
Examples 4,
Synthesis of (method two)
Step 1
Adding 0.1mol of (I-16-a), 100ml of glacial acetic acid and 5% of Pt/C10g into a reaction bottle, stirring, hydrogenating for 6 hours under normal pressure, filtering to remove the catalyst, evaporating the solvent, adding 50ml of toluene for recrystallization, and obtaining (I-17-a) with the yield of 50%
Step 2
Adding 0.1mol of (I-17-a), 30ml of toluene (solvent) and 30ml of isooctane (solvent) into a reaction bottle, adding 14g of 1, 3-propanedithiol (reactant), heating the suspension to 50 ℃ under stirring, adding 19.2g of trifluoromethanesulfonic acid (reactant) within 30 minutes, heating to reflux after the addition is finished, separating out the generated water, cooling to 90 ℃ after water is separated, adding 100ml of methyl tert-butyl ether (solvent) within 45 minutes between 70 and 90 ℃, continuously cooling, precipitating crystals, filtering under the protection of nitrogen, washing the obtained crystals with methyl tert-butyl ether (solvent) (25 ml multiplied by 4), and drying in vacuum to obtain orange crystals (dithiane trifluoromethanesulfonate).
Step 3
A mixed solution of 0.1mol of 3,4, 5-trifluorophenol (reactant), 0.1mol of triethylamine (reactant) and 130ml of dichloromethane (solvent) was charged into a reaction flask and cooled to-70 ℃ and a solution of the above 0.1mol of the above-mentioned crystals (reactant) of dithiane trifluoromethanesulfonate in 120ml of dichloromethane (solvent) was added dropwise over 45 minutes, and after stirring at this temperature for one hour, 0.4mol of NEt was added within 5 minutes33HF (reactant). Then, 30ml of a dichloromethane (solvent) solution of 0.4mol of liquid bromine (reactant) was added at-70 ℃ for one hour, and the reaction was continued at-70 ℃ for one hour, and the temperature was raised to 0 ℃ to pour the reaction solution into 32% of a 160ml aqueous sodium hydroxide solution (pH adjustment) and 300g of ice, and the pH of the reaction solution was adjusted to 5 to 8 by dropwise addition of about 45g of 32% aqueous sodium hydroxide solution. After separation, the aqueous phase is extracted with 80ml of dichloromethane (solvent), the combined organic phases are filtered over 4g of kieselguhr (decolourant), washed with water and the solvent is evaporated under reduced pressure. The crude product obtained was subjected to column chromatography and then recrystallized from petroleum ether (solvent) to obtain a white crystalline product (i-17) in a yield of 45%, GC: 99.5 percent.
The structure confirmation data for this product are as follows:
MP：35℃；
MS：m/s%444（45.3），296(56.8),148(37.4),69(100),
1H-NMR：δ（ppm）0.90(t,3H),1.27(m,10H),1.45(m,12H)1.72(m,2H),1.96(m,3H),2.48(，m，1H),6.89(m,2H)
as can be seen from the above, the product has a correct structure and is a compound represented by formula I-17.
The liquid crystal properties of the compound are shown below:
△ε：9.5（20℃，589nm）
△n：0.065（20℃，1000Hz）
from the above, the compound has photo-thermal stability, wide liquid crystal state temperature range, better low-temperature intersolubility and larger dielectric anisotropy Delta epsilon, and can realize lower threshold voltage and low rotational viscosity gamma when an optical device is used1The liquid crystal composition material and the display performance can be improved, and the method has important significance for realizing the quick response of the display.
Referring to examples 1-4, only the groups in the reactant formulae were replaced according to the formula of the product to give the compounds of formula I:
example 3 liquid-crystalline mixture a
Uniformly mixing the components in parts by weight to obtain a liquid crystal mixture a provided by the invention:
the properties of the mixture are shown below:
△n：0.105；
cp[℃]：95℃；
△ε：7.2；
γ1：65。
from the above, the mixture has a suitably high clearing point, a suitably high optical anisotropy, a relatively low rotational viscosity and a relatively high response speed, and is suitable for use in liquid crystal displays, particularly TN-TFT and IPS-TFT display modes.
Example 4 liquid-crystalline mixture b
Uniformly mixing the components in parts by weight to obtain a liquid crystal mixture b provided by the invention:
the properties of the mixture are shown below:
△n：0.110；
cp[℃]：94℃；
△ε：7.0；
γ1：60。
from the above, the mixture has a high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and can be applied to liquid crystal displays.
Example 5 liquid-crystalline mixture c
Uniformly mixing the components in parts by weight to obtain a liquid crystal mixture c provided by the invention:
the properties of the mixture are shown below:
△n：0.095；
cp[℃]：100℃；
△ε：8.0；
γ1：78。
from the above, the mixture has a high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and can be applied to liquid crystal displays.
Example 6 liquid-crystalline mixture d
Uniformly mixing the components in parts by weight to obtain a liquid crystal mixture d provided by the invention:
weight percent of monomer
（%）
The properties of the mixture are shown below:
△n：0.090；
cp[℃]：85℃；
△ε：8.5；
γ1：55。
from the above, the mixture has a high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and can be applied to liquid crystal displays.
Example 7 liquid-crystalline mixture e
Uniformly mixing the components in parts by weight to obtain a liquid crystal mixture e provided by the invention:
the properties of the mixture are shown below:
△n：0.100；
cp[℃]：105℃；
△ε：6.5；
γ1：70。
from the above, the mixture has a high clearing point, appropriate optical anisotropy, low rotational viscosity and fast response speed, and can be applied to liquid crystal displays.
Claims (9)
1. A compound of the formula I, wherein,
In the formula I, R1And R2Are selected from any one of the groups a, b or c:
a. selected from H, Cl, F, -CN, -OCN, -OCF3、-CF3、-CHF2、-CH2F、-OCHF2、-SCN、-NCS、-SF5At least one of an alkyl group having 1 to 15 carbon atoms in total, an alkoxy group having 1 to 15 carbon atoms in total, an alkenyl group having 2 to 15 carbon atoms in total, and an alkenyloxy group having 2 to 15 carbon atoms in total;
b. containing-CH2One or at least two of said groups a of-are not adjacent-CH2-a group substituted with at least one of the following groups without direct connection of oxygen atoms: -CH = CH-, -C ≡ C-, -COO-, -OOC-, cyclobutane, -O-, and-S-;
c. a group obtained by substituting at least one hydrogen of the groups a or b with fluorine or chlorine;
Z1and Z2Are all single bonds, -CH2-、-CH2-CH2-、-（CH2）3-、-(CH2)4-、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CF2CH2-、-CH2CF2-、-C2F4-or-CF ═ CF —;
a. b, c and d are integers of 0-3, and a + b + c + d is less than or equal to 5;
when a or b or c or d is 2 or 3,the radicals indicated are all identical or different.
2. The compound of claim 1, wherein: the compound shown in the formula I is any one of compounds shown in formulas I-1 to I-4:
wherein the compound shown in the formula I-1 is specifically any one of the following compounds:
the compound shown in the formula I-2 is specifically any one of the following compounds:
the compound shown in the formula I-3 is specifically any one of the following compounds:
the compound shown in the formula I-4 is specifically any one of the following compounds:
in the formulae I-1 to I-13, R1、R2、
Is as defined in claim 1;
L1to L8Are both selected from any one of hydrogen and fluorine.
3. Liquid crystal mixtures comprising compounds according to any of claims 1 to 2.
4. A liquid crystal mixture consisting of a compound according to claim 1 or 2 and a compound of formula II to IV:
Formula IV
In the formulae II to IV, R1、R2And R3At least one selected from the group consisting of a hydrogen atom, a halogen, -CN, an alkyl group having 1 to 7 carbon atoms in total, an alkoxy group having 1 to 7 carbon atoms in total, an alkenyl group having 2 to 7 carbon atoms in total, and a fluoroalkoxy group having 1 to 5 carbon atoms in total;
z is selected from single bond, -CH2-CH2-、-CH=CH-、-C≡C-、-COO-、-OOC-、-OCH2-、-CH2O-、-CF2O-and-OCF2-at least one of;
Y1and Y2Both selected from at least one of H and F;
p is an integer of 0 to 2;
when the P is 2, the compound is,
the same or different.
5. Liquid crystal mixture according to claim 4, characterized in that: the mass ratio of the compounds shown in the formulas I to IV is 0-40: 4-50: 5-50: 3-45, and the mass of the compound shown in the formula I is not 0.
6. A liquid-crystal mixture according to claim 4 or 5, characterized in that: the liquid crystal mixture is specifically the following liquid crystal mixtures a, b, c, d or e:
the liquid crystal mixture a comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture a specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture b comprises or consists of the following components in parts by mass:
the liquid crystal mixture b specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture c comprises or consists of the following components in parts by mass:
the liquid crystal mixture c specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture d comprises or consists of the following components in parts by mass:
the liquid crystal mixture d specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture e comprises the following components in parts by mass or consists of the following components in parts by mass:
the liquid crystal mixture e specifically comprises the following components in parts by mass or consists of the following components in parts by mass:
7. use of a liquid-crystal compound of the formula I as claimed in any of claims 1 to 2 or of a liquid-crystal mixture as claimed in any of claims 4 to 6 for the preparation of liquid-crystal display materials or electro-optical liquid-crystal displays.
8. A liquid crystal display material or electro-optical liquid crystal display comprising at least one of the liquid crystal compounds of formula I according to claims 1 to 2 or the liquid crystal mixtures according to claims 4 to 6.
9. The display according to claim 7 or 8, wherein: the electro-optical liquid crystal display is a TN type display, a VA type display, an IPS type display or a PDLC type display.
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| CN1720314A (en) * | 2002-12-02 | 2006-01-11 | 默克专利股份有限公司 | New cyclobutane derivatives |
| US7846514B2 (en) * | 2007-01-24 | 2010-12-07 | Chisso Corporation | Liquid crystal compound, liquid crystal composition and, liquid crystal display device |
| CN103320144A (en) * | 2012-06-20 | 2013-09-25 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing dihydrobenzofuran and preparation method and application thereof |
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| CN1720314A (en) * | 2002-12-02 | 2006-01-11 | 默克专利股份有限公司 | New cyclobutane derivatives |
| US7846514B2 (en) * | 2007-01-24 | 2010-12-07 | Chisso Corporation | Liquid crystal compound, liquid crystal composition and, liquid crystal display device |
| CN103320144A (en) * | 2012-06-20 | 2013-09-25 | 石家庄诚志永华显示材料有限公司 | Liquid crystal compound containing dihydrobenzofuran and preparation method and application thereof |
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| CN104045527A (en) * | 2014-04-23 | 2014-09-17 | 石家庄诚志永华显示材料有限公司 | Difluoromethoxy-bridged derivative and preparation method and application |
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