CN103534335B - 液晶化合物 - Google Patents
液晶化合物 Download PDFInfo
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- CN103534335B CN103534335B CN201280009391.2A CN201280009391A CN103534335B CN 103534335 B CN103534335 B CN 103534335B CN 201280009391 A CN201280009391 A CN 201280009391A CN 103534335 B CN103534335 B CN 103534335B
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- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 110
- 150000001875 compounds Chemical class 0.000 title claims abstract description 58
- 239000000203 mixture Substances 0.000 claims abstract description 64
- 125000004432 carbon atom Chemical group C* 0.000 claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims description 17
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 239000012769 display material Substances 0.000 claims description 13
- -1 oxaalkyl groups Chemical group 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 229910052731 fluorine Inorganic materials 0.000 claims description 7
- 125000001424 substituent group Chemical group 0.000 claims description 5
- 125000003342 alkenyl group Chemical group 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 2
- 125000001153 fluoro group Chemical group F* 0.000 claims description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 2
- 125000000262 haloalkenyl group Chemical group 0.000 claims description 2
- 125000005291 haloalkenyloxy group Chemical group 0.000 claims description 2
- 125000004438 haloalkoxy group Chemical group 0.000 claims description 2
- 125000001188 haloalkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 83
- 239000002904 solvent Substances 0.000 description 70
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 239000000376 reactant Substances 0.000 description 28
- 239000000047 product Substances 0.000 description 27
- 239000000243 solution Substances 0.000 description 27
- 238000006243 chemical reaction Methods 0.000 description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 24
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 238000010992 reflux Methods 0.000 description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 239000013078 crystal Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 13
- 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 12
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 11
- 238000001514 detection method Methods 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000012074 organic phase Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 9
- 238000001704 evaporation Methods 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 229910052749 magnesium Inorganic materials 0.000 description 9
- 239000012071 phase Substances 0.000 description 9
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 8
- 229910000564 Raney nickel Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000003208 petroleum Substances 0.000 description 8
- 239000013256 coordination polymer Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 5
- 239000001569 carbon dioxide Substances 0.000 description 5
- 239000012043 crude product Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000003112 inhibitor Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 230000004224 protection Effects 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 4
- AEBWATHAIVJLTA-UHFFFAOYSA-N 1,2,3,3a,4,5,6,6a-octahydropentalene Chemical compound C1CCC2CCCC21 AEBWATHAIVJLTA-UHFFFAOYSA-N 0.000 description 4
- 239000007818 Grignard reagent Substances 0.000 description 4
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 4
- 238000007259 addition reaction Methods 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 description 4
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 4
- 150000004795 grignard reagents Chemical class 0.000 description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 4
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical class [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 3
- JSENTYXHEBMPIU-UHFFFAOYSA-N Fc1cc(F)cc(c1)C1CC2CC(=O)CC2C1 Chemical compound Fc1cc(F)cc(c1)C1CC2CC(=O)CC2C1 JSENTYXHEBMPIU-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000002274 desiccant Substances 0.000 description 3
- 125000005701 difluoromethyleneoxy group Chemical group FC(F)([*:1])O[*:2] 0.000 description 3
- 235000019253 formic acid Nutrition 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 3
- 0 *C(C1)CC(C2)C1CC2c1ccc(C(CC(F)=C2*C(CC3F)=CC(F)=C3F)C=C2F)c(F)c1 Chemical compound *C(C1)CC(C2)C1CC2c1ccc(C(CC(F)=C2*C(CC3F)=CC(F)=C3F)C=C2F)c(F)c1 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000007868 Raney catalyst Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- GUYWOVXWSWXETF-UHFFFAOYSA-N 1-(4-bromophenyl)-3,5-difluorobenzene Chemical group FC1=CC(F)=CC(C=2C=CC(Br)=CC=2)=C1 GUYWOVXWSWXETF-UHFFFAOYSA-N 0.000 description 1
- JHLKSIOJYMGSMB-UHFFFAOYSA-N 1-bromo-3,5-difluorobenzene Chemical compound FC1=CC(F)=CC(Br)=C1 JHLKSIOJYMGSMB-UHFFFAOYSA-N 0.000 description 1
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 1
- ZRTWIJKGTUGZJY-UHFFFAOYSA-N 3,4,5-trifluorophenol Chemical compound OC1=CC(F)=C(F)C(F)=C1 ZRTWIJKGTUGZJY-UHFFFAOYSA-N 0.000 description 1
- UPJMWRYBLNHWQS-UHFFFAOYSA-N 4-methylbenzenesulfonic acid;toluene Chemical compound CC1=CC=CC=C1.CC1=CC=C(S(O)(=O)=O)C=C1 UPJMWRYBLNHWQS-UHFFFAOYSA-N 0.000 description 1
- TVEQPQIWBJSRPK-UHFFFAOYSA-N CCCC1=CC2CC(CC2C1)C1=CC(F)=CC(F)=C1 Chemical compound CCCC1=CC2CC(CC2C1)C1=CC(F)=CC(F)=C1 TVEQPQIWBJSRPK-UHFFFAOYSA-N 0.000 description 1
- UKXXJLYOPNRFKY-UHFFFAOYSA-N CCCC1CC2CC(CC2C1)C1=CC(F)=CC(F)=C1 Chemical compound CCCC1CC2CC(CC2C1)C1=CC(F)=CC(F)=C1 UKXXJLYOPNRFKY-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- JNCMHMUGTWEVOZ-UHFFFAOYSA-N F[CH]F Chemical compound F[CH]F JNCMHMUGTWEVOZ-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000006856 Wolf-Kishner-Huang Minlon reduction reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- FIGYBMDNOMRNFK-UHFFFAOYSA-N dithian-1-ium trifluoromethanesulfonate Chemical compound FC(S(=O)(=O)[O-])(F)F.[SH+]1SCCCC1 FIGYBMDNOMRNFK-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- WVEPPXXXZXVMAR-UHFFFAOYSA-N formic acid;toluene Chemical compound OC=O.CC1=CC=CC=C1 WVEPPXXXZXVMAR-UHFFFAOYSA-N 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- UCDWWJKPBQZZNT-UHFFFAOYSA-N magnesium;oxolane Chemical compound [Mg].C1CCOC1 UCDWWJKPBQZZNT-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- ZPVFWPFBNIEHGJ-UHFFFAOYSA-N n-hexyl methyl ketone Natural products CCCCCCC(C)=O ZPVFWPFBNIEHGJ-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000004812 organic fluorine compounds Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- FZJCXIDLUFPGPP-UHFFFAOYSA-N propan-2-ol;toluene Chemical compound CC(C)O.CC1=CC=CC=C1 FZJCXIDLUFPGPP-UHFFFAOYSA-N 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- WWAYLSXXLXIQNN-UHFFFAOYSA-N spiro[1,3,3a,4,6,6a-hexahydropentalene-5,2'-1,3-dioxolane]-2-one Chemical compound C1C2CC(=O)CC2CC21OCCO2 WWAYLSXXLXIQNN-UHFFFAOYSA-N 0.000 description 1
- 125000005415 substituted alkoxy group Chemical group 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
-
- 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
- C07D—HETEROCYCLIC COMPOUNDS
- C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
- C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
- C07D309/04—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D309/06—Radicals substituted by oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D317/00—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D317/08—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3
- C07D317/72—Heterocyclic compounds containing five-membered rings having two oxygen atoms as the only ring hetero atoms having the hetero atoms in positions 1 and 3 spiro-condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09K19/321—Compounds containing a bicyclo [2,2,2] octane ring
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/42—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
- 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
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/14—All rings being cycloaliphatic
- C07C2602/22—All rings being cycloaliphatic the ring system containing eight carbon atoms, e.g. pentalene
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/44—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing eight carbon atoms
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- 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
- C09K2019/0444—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group
- C09K2019/0466—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit characterized by a linking chain between rings or ring systems, a bridging chain between extensive mesogenic moieties or an end chain group the linking chain being a -CF2O- chain
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/08—Non-steroidal liquid crystal compounds containing at least two non-condensed rings
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Abstract
本发明公开了一种液晶化合物。该化合物结构通式如式I所示。该类化合物具有良好的热稳定性和对紫外光的稳定性、较大的正介电各向异性△ε,光学器件使用时可实现较低的阈值电压,对实现显示器的快速响应具有重要意义,故非常适合用于调配液晶混合物。含有此类液晶单体的液晶混合物可应用于多种显示器,尤其是适用于TN-TFT和STN显示器,也可以用于IPS、VA显示器。
Description
技术领域
本发明属于液晶化合物及应用领域,涉及一种液晶化合物,尤其是涉及一种含有双环(3,3,0)辛烷和二氟亚甲氧基连接基团(-CF2O-)的液晶化合物及其制备方法与应用。
背景技术
目前,液晶化合物的应用范围拓展地越来越广,其可应用于多种类型的显示器、电光器件、传感器等中。用于上述显示领域的液晶化合物的种类繁多,其中向列相液晶应用最为广泛。向列相液晶已经应用在无源TN、STN矩阵显示器和具有TFT有源矩阵的系统中。
而对于超扭曲(STN)用的液晶混合物,常常需要有较大的多路转换性、较低的阈值电压、较宽的向列相范围。而作为将在STN混合物中使用的液晶单体,进一步改善其液晶性能、拓宽应用范围仍是有必要的。
对于薄膜晶体管技术(TFT-LCD)应用领域,近年来市场虽然已经非常巨大,技术也逐渐成熟,但人们对显示技术的要求也在不断的提高,尤其是在实现快速响应,降低驱动电压以降低功耗等方面。液晶材料作为液晶显示器重要的光电子材料之一,对改善液晶显示器的性能发挥重要的作用。
作为液晶材料,需要具有良好的化学和热稳定性以及对电场和电磁辐射的稳定性。而作为薄膜晶体管技术(TFT-LCD)用液晶材料,不仅需要具有如上稳定性外,还应具有较宽的向列相、较低的双折射率、非常高的电阻率、良好的抗紫外线性能、高电荷保持率以及低蒸汽压等性能。
为了实现改善液晶显示性能,另外开发具有较低的旋转粘度γ1(甚至是在低温下),较高的介电各向异性Δε的混合液晶具有重要意义。因此开发合成具有此性能的液晶单体在未来的研究方向是重中之重。
发明公开
本发明的目的是提供一种液晶化合物,尤其是一种含有双环(3,3,0)辛烷和二氟亚甲氧基连接基团(-CF2O-)的液晶化合物及其制备方法与应用。
本发明提供的液晶化合物,也即含有双环(3,3,0)辛烷和二氟亚甲氧基连接基团(-CF2O-)的液晶化合物,其结构通式如式I所示,
所述式I中,R1和R2为如下A或B所示基团:
A、选自碳原子总数为1-10的烷基、氟取代的碳原子总数为1-10的烷基、氯取代的碳原子总数为1-10的烷基、碳原子总数为1-10的烷氧基、氟取代的碳原子总数为1-10的烷氧基、氯取代的碳原子总数为1-10的烷氧基、H、Cl、F、CN、OCN、OCF3、CF3、CHF2、OCHF2、SCN、NCS和SF5中的至少一种;
B、将所述A中含-CH2-的任意基团中至少一个-CH2-被如下基团中的至少一种取代而得的基团:-CH=CH-、-C≡C-、-COO-、-OOC-、环丁烷和-O-;
所述A中含-CH2-的任意基团为碳原子总数为1-10的烷基、氟取代的碳原子总数为1-10的烷基、氯取代的碳原子总数为1-10的烷基、碳原子总数为1-10的烷氧基、氟取代的碳原子总数为1-10的烷氧基或氯取代的碳原子总数为1-10的烷氧基;
所述A1、A2和A3均选自下述基团中的至少一种:
所述L1和L2均选自单键、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-OCH2-、-CH2O-、-OCF2-、-CH2CH2-、-CF2CH2-、-CH2CF2-、-C2F4-、-CF=CF-和-(CH2)4-中的至少一种;
所述a和b均选自0-3的整数中的任意一个,且a+b≤4;
所述a和b均为2或3时,结构单元A1-L1中,A1相同或不同,L1相同或不同;结构单元A2-L2中,A2相同或不同,L2相同或不同。
具体的,所述式I所示化合物为式Ia所示化合物,
所述式Ia中,R1、R2、A1、A2、A3、a和b与前述定义相同。
更具体的,所述式I所示化合物为式I1至式I11所示化合物中的任意一种,
所述式I1至式I11中,所述R11均选自氢、碳原子总数为1-10的直链烷基和碳原子总数为1-10的烷氧基中的至少一种,所述-(F)表示苯环上有氟原子取代基或氢。
式I所示液晶化合物可通过如下合成路线1和2制备得到(其中中间体7,7-乙二氧基-3-双环[3.3.0]辛酮的合成方法依CN03136662.7中所述,二氟亚甲氧基(-CF2O-)的引入在《当代有机氟化学》(原著P.Kirsch,朱士正,吴永明译)P287-288中给出):
合成路线1:(制备R1不为氢的所述式I所示化合物)
该方法具体包括如下步骤:
1)将(L1-A1)a-Br与镁在四氢呋喃中进行回流反应,加热回流1小时,至镁屑几乎全部消失,反应完毕得到含有(L1-A1)a-MgBr格氏试剂的溶液,再将的四氢呋喃溶液滴加至前述所得(L1-A1)a-MgBr的溶液中,滴毕,回流2小时,降温至0℃,倒入有浓盐酸的冰水中,搅拌水解2分钟,分出水相,乙酸乙酯提取一次,合并有机相,饱和食盐水洗两次至中性,无水硫酸钠干燥,浓缩除去溶剂,将所得产物、催化剂对甲苯磺酸、阻聚剂2,6-二叔丁基对甲酚和溶剂甲苯混匀进行回流反应脱水5小时,降至室温,分液弃去下层的乙二醇层,甲苯层依次用饱和碳酸氢钠水溶液和去离子水洗涤,甲苯层用无水硫酸钠干燥4小时,过滤,蒸除溶剂反应完毕得到
2)将所述步骤1)所得溶剂异丙醇和甲苯、拉尼镍催化剂和氢气进行常压氢化反应,反应完毕得到
3)将所述步骤2)所得和甲酸及溶剂甲苯混匀进行缩酮水解反应,反应完毕得到
4)向镁和四氢呋喃中滴加R1-Br得到格式试剂后,加入所述步骤3)所得与R1-Br进行回流加成反应2小时后,滴加盐酸进行室温水解反应半小时后,倒入水中,并加入溶剂甲苯,分液,有机层水洗至中性,蒸除溶剂,把催化剂对甲苯磺酸,阻聚剂2,6-二叔丁基对甲酚、溶剂甲苯和乙二醇及上述产物,置于三口瓶中加热回流脱水5小时后降至室温,分液弃去下层的乙二醇层,甲苯层依次用饱和碳酸氢钠水溶液和去离子水洗涤,甲苯层用无水硫酸钠干燥4小时,过滤,蒸除溶剂得粗品,用2倍异丙醇和石油醚(1∶1)重结晶两次得白色晶体即为
5)将所述步骤4)所得溶剂异丙醇和甲苯、拉尼镍催化剂和氢气进行常压氢化反应,反应完毕得到
6)将所述步骤5)所得和溶剂四氢呋喃于反应容器中安装密封搅拌,通氮气置换空气,降温至-70℃,滴加丁基锂,加完后20分钟,通入干燥的二氧化碳气体,至饱和,在此温度下进行锂试剂与二氧化碳进行加成反应2小时,将此反应液倒入有浓盐酸和水的烧杯中水解,分液,乙酸乙酯提取水相一次,合并有机相,饱和食盐水洗至中性,无水硫酸钠干燥,浓缩除尽溶剂,得到浅黄色固体,用异丙醇重结晶一次,得到
7)将所述步骤6)所得溶剂甲苯和异辛烷、1,3-丙二硫醇混合,将上述悬浮液加热至50℃,在30分钟内加入三氟甲磺酸,加完后升温至回流进行缩合反应,分出生成的水,待分净水后,冷却降温至90℃,在70-90℃之间45分钟内加入溶剂甲基叔丁基醚,继续降温,析出晶体,在氮气保护下过滤,得到的晶体用甲基叔丁基醚洗涤,真空干燥后,将所得产物的二氯甲烷溶液滴加到由三乙胺、溶剂二氯甲烷和组成的混合液中,45分钟加完,在此温度搅拌一小时后,5分钟内加入NEt3·3HF,然后在-70℃下,一小时内加入液溴的二氯甲烷溶液进行反应,然后在-70℃下继续反应一小时,升温至0℃,将反应液倒入32%的氢氧化钠水溶液和300g冰中,调节反应液的pH值至5~8后,分液后水相用80ml二氯甲烷提取,合并有机相用硅藻土过滤,水洗,减压下蒸干溶剂,得到所述R1不为氢的所述式I所示化合物。
合成路线2:(制备R1为氢的所述式I所示化合物)
该方法具体包括如下步骤:
1)将(L1-A1)a-Br与镁在四氢呋喃中进行回流反应,加热回流1小时,至镁屑几乎全部消失,反应完毕得到含有(L1-A1)a-MgBr格氏试剂的溶液,再将的四氢呋喃溶液滴加至前述所得(L1-A1)a-MgBr的溶液中,滴毕,回流2小时,降温至0℃,倒入有浓盐酸的冰水中,搅拌水解2分钟,分出水相,乙酸乙酯提取一次,合并有机相,饱和食盐水洗两次至中性,无水硫酸钠干燥,浓缩除去溶剂,将所得产物、催化剂对甲苯磺酸、阻聚剂2,6-二叔丁基对甲酚和溶剂甲苯混匀进行回流反应脱水5小时,降至室温,分液弃去下层的乙二醇层,甲苯层依次用饱和碳酸氢钠水溶液和去离子水洗涤,甲苯层用无水硫酸钠干燥4小时,过滤,蒸除溶剂反应完毕得到
2)将所述步骤1)所得溶剂异丙醇和甲苯、拉尼镍催化剂和氢气进行常压氢化反应,反应完毕得到
3)将所述步骤2)所得和甲酸及溶剂甲苯混匀进行缩酮水解反应,反应完毕得到
4)将所述步骤3)所得80%水合肼、一缩二乙二醇溶剂、氢氧化钾催化剂混匀进行加热回流,发生黄鸣龙还原反应,加热回流5小时后,改为蒸馏,蒸出过量的水合肼至190-200℃,然后再回流3小时,降温至室温,反应完毕得到
5)将所述步骤4)所得和溶剂四氢呋喃于反应容器中安装密封搅拌,通氮气置换空气,降温至-70℃,滴加丁基锂,加完后20分钟,通入干燥的二氧化碳气体,至饱和,在此温度下进行锂试剂与二氧化碳进行加成反应2小时,将此反应液倒入有浓盐酸和水的烧杯中水解,分液,乙酸乙酯提取水相一次,合并有机相,饱和食盐水洗至中性,无水硫酸钠干燥,浓缩除尽溶剂,得到浅黄色固体,用异丙醇重结晶一次,得到
6)将所述步骤5)所得溶剂甲苯和异辛烷、1,3-丙二硫醇混合,将上述悬浮液加热至50℃,在30分钟内加入三氟甲磺酸,加完后升温至回流进行缩合反应,分出生成的水,待分净水后,冷却降温至90℃,在70-90℃之间45分钟内加入溶剂甲基叔丁基醚,继续降温,析出晶体,在氮气保护下过滤,得到的晶体用甲基叔丁基醚洗涤,真空干燥后,将所得产物的二氯甲烷溶液滴加到由三乙胺、溶剂二氯甲烷和组成的混合液中,45分钟加完,在此温度搅拌一小时后,5分钟内加入NEt3·3HF,然后在-70℃下,一小时内加入液溴的二氯甲烷溶液进行反应,然后在-70℃下继续反应一小时,升温至0℃,将反应液倒入32%的氢氧化钠水溶液和300g冰中,调节反应液的pH值至5~8后,分液后水相用80ml二氯甲烷提取,合并有机相用硅藻土过滤,水洗,减压下蒸干溶剂,得到所述R1不为氢的所述式I所示化合物,也即
上述两合成路线中,各反应条件具体如下:
e:四氢呋喃 镁屑 回流;对甲苯磺酸 甲苯 回流分水
f:异丙醇 甲苯 钯碳 常压氢化
g:甲酸 甲苯 30℃
h:镁屑 四氢呋喃 回流,对甲苯磺酸 甲苯 回流
i:异丙醇 甲苯 拉尼镍催化剂 常压氢化
j:BuLi-70℃ CO2
k:丙二硫醇 三氟甲磺酸 甲苯 异辛烷 回流分水,二氯甲烷 -70℃ 三乙胺NEt3·3HF 溴 -70℃
l:80%水合肼 一缩二乙二醇 氢氧化钾
其中,合成路线1,2中R1、R2、A1、A2、A3、A4、L1、L2、L3、a和b所代表的含义与前述式I中的定义相同。
另外,包含组分A也即前述式I所示所述化合物中至少一种的液晶混合物,也属于本发明的保护范围。所述组分A中,式I所示化合物为1-5种,优选1-3种。
所述液晶混合物还包含组分B;
所述组分B为下述化合物式II-式XIV中的至少一种:
所述式II-式XI中,所述R3和R4均选自碳原子总数为1-9的正烷基、氟烷基、烷氧基、氧杂烷基、链烯基和链烯氧基中的至少一种;
所述Z均选自单键、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-CH2O-、-OCF2-、-CH2CH2-、-CF2CH2-、-C2F4-和-(CH2)4-中的至少一种;
Y均为H或F;
X均为F、Cl、碳原子总数为1-9的卤代烷基、碳原子总数为1-9的卤代链烯基、碳原子总数为1-9的链烯基、碳原子总数为1-9的卤代烷氧基、碳原子总数为1-9的卤代链烯基氧基和碳原子总数为1-9的烷基中的至少一种;
n均为0或1;
所述组分B具体为如下结构式的化合物中的至少一种:
所述组分A与所述组分B的质量比为1-70∶100,优选2-40∶100,更优选13∶100。
具体的,所述液晶混合物由所述组分A和所述组分B组成;
所述组分A与所述组分B的质量比为1-70∶100,优选2-40∶100,更优选13∶100。
具体的,所述液晶混合物具体为如下组成混合物a或b:
混合物a由组分A和组分B组成:
所述组分A为
所述组分B由如下质量比的各化合物组成:
其中,所述组分A与组分B的质量比为13∶100;
混合物b由组分A和组分B组成:
所述组分A由和组成;
所述组分B由如下质量比的各化合物组成:
其中,所述组分A中,与组分B的质量比为6∶100;
与组分B的质量比为3∶100;
与组分B的质量比为4∶100。
显而易见的,由于双环(3,3,0)辛烷结构化学性质稳定,也很难被水解、氧化或开环,所以此类液晶混合物具有良好的对热和紫外线的稳定性。
实施发明的最佳方式
下面实施例用于解释本发明,但本发明不仅限于下面实施例。下面实施例中GC表示气相色谱纯度,HPLC表示液相色谱纯度,MP表示熔点,CP表示清亮点,MS表示质谱,1H-NMR表示核磁氢谱,Δε表示介电各向异性,Δn表示光学各向异性,Vth表示阈值电压,检测温度为25℃。
实施例1、制备
步骤1:
3L的三口瓶中加入30g镁屑(反应物)和250ml无水四氢呋喃(溶剂),在500ml的滴液漏斗中加入220g 3,5-二氟溴苯(反应物)(99.7%)和300ml无水四氢呋喃(溶剂)的溶液,滴加15ml溶液,加热引发反应。缓慢的滴加该四氢呋喃溶液,维持轻微的回流。滴毕,加热回流1小时,至镁屑几乎全部消失。滴加182g7,7-乙二氧基-3-双环[3.3.0]辛酮(反应物)和400ml四氢呋喃(溶剂)的溶液,滴毕,回流2小时。降温至0℃左右,倒入有110ml浓盐酸(反应物)的500g的冰水(溶剂)中,搅拌水解2分钟,分出水相,100ml乙酸乙酯(溶剂)提取一次,合并有机相,饱和食盐水洗两次至中性,无水硫酸钠(干燥剂)干燥,浓缩除去溶剂得到浅黄色固体。
把20g对甲苯磺酸(催化剂),2g 2,6-二叔丁基对甲酚(阻聚剂),1000ml甲苯(溶剂),200ml乙二醇(溶剂)及上述浅黄色固体产物,置于2L三口瓶中加热回流脱水五小时,降至室温,分液弃去下层的乙二醇层,甲苯层依次用200ml饱和碳酸氢钠水溶液和500ml去离子水(溶剂)洗涤,甲苯层用无水硫酸钠(干燥剂)干燥4小时,过滤,蒸除溶剂得粗品,粗品用2倍异丙醇和石油醚(1∶1)重结晶两次得白色晶体139g(1-a)。
步骤2:
5L单口瓶中加入139g(1-a)(反应物),260ml异丙醇(溶剂),300ml甲苯(溶剂),湿重50g拉尼镍(催化剂)(用量为底物重量的1-20%)催化剂,常压氢化5小时,吸氢至理论量,小心地过滤除去拉尼镍催化剂,浓缩除净溶剂,得到139g微黄色固体(1-b),mp:55.5℃ GC:99.5%。
步骤3:
1L的单口瓶中加入40g实施1步骤2得到的3,3-乙二氧基-7-(3’,4’-二氟苯基)-双环[3.3.0]辛烷(1-b)(反应物),500ml 88%甲酸(反应物),300ml甲苯(溶剂),室温搅拌进行缩酮水解反应12小时,分液,甲苯层水洗至中性,无水Na2SO4干燥4小时,过滤,蒸除溶剂得32g 3-氧代-7-(3’,5’-二氟苯基)-双环[3.3.0]辛烷(1-c),GC:99.0%。
步骤4:
1L的三口瓶中加入8g镁屑(反应物)和300ml无水四氢呋喃(溶剂),滴加37g溴丙烷(反应物)(分析纯)制成格式试剂,加入32g实施例1步骤3合成的化合物3-氧代-7-(3’,5’-二氟苯基)-双环[3.3.0]辛烷(1-c)(反应物),回流加成反应2小时,滴加72ml 6M的盐酸(反应物),室温下水解半小时。倒入水中,并加入150ml甲苯(溶剂),分液,有机层水洗至中性,蒸除溶剂,把5g对甲苯磺酸(催化剂),0.5g 2,6-二叔丁基对甲酚(阻聚剂),200ml甲苯(溶剂),50ml乙二醇(溶剂)及上述产物,置于500ml三口瓶中加热回流脱水五小时,降至室温,分液弃去下层的乙二醇层,甲苯层依次用50ml饱和碳酸氢钠水溶液和50ml去离子水(溶剂)洗涤,甲苯层用无水硫酸钠(干燥剂)干燥4小时,过滤,蒸除溶剂得粗品,用2倍异丙醇和石油醚(1∶1)(溶剂)重结晶两次得白色晶体3-丙基-7-(3’,5’-二氟苯基)-2-双环[3.3.0]辛烯(1-d)21g。
步骤5:
1L单口瓶中加入21g(1-d),150ml异丙醇(溶剂),湿重50g拉尼镍(催化剂)(用量在底物重量的1-20%之间)催化剂,常压氢化5小时,吸氢至理论量,小心地过滤除去拉尼镍催化剂,浓缩除净溶剂,得到微黄色固体3-丙基-7-(3’,5’-二氟苯基)双环[3.3.0]辛烷(1-e)21g,GC:99.1%。
步骤6:
500ml三口瓶中加入实施例1步骤5得到的21g(1-e)(反应物),150ml四氢呋喃(溶剂),安装密封搅拌,通氮气置换空气,降温至-70℃,滴加0.1mol浓度为2.5M的丁基锂(反应物),加完后20分钟,通入干燥的二氧化碳(反应物)气体,至饱和,在此温度下进行加成反应2小时,将此反应液倒入有20ml浓盐酸(反应物)100ml水(溶剂)的烧杯中水解,分液,50ml乙酸乙酯(溶剂)提取水相一次,合并有机相,饱和食盐水洗至中性,无水硫酸钠干燥,浓缩除尽溶剂,得到浅黄色固体,用异丙醇重结晶一次,得到18g白色晶体(1-f)。
步骤7:
向250ml三口瓶中加入30.8g(1-f)(反应物),30ml甲苯(溶剂)和30ml异辛烷(溶剂),加入14g 1,3-丙二硫醇(反应物),搅拌下将上述悬浮液加热至50℃,在30分钟内加入三氟甲磺酸(反应物)19.2g,加完后升温至回流进行缩合反应,分出生成的水,待分净水后,冷却降温至90℃,在70-90℃之间45分钟内加入甲基叔丁基醚(溶剂)100ml,继续降温,析出晶体,在氮气保护下过滤,得到的晶体用甲基叔丁基醚(溶剂)(25ml×4)洗涤,真空干燥得到晶体45g(二噻烷三氟甲磺酸盐)。
在500ml三口瓶中加入14.8g 3,4,5-三氟苯酚(反应物),10.8g三乙胺(反应物)和130ml二氯甲烷(溶剂)的混合溶液并冷却至-70℃,滴加上述45g晶体的120ml二氯甲烷(溶剂)的溶液,45分钟加完,在此温度搅拌一小时后,5分钟内加入73.5mlNEt3·3HF(反应物)。然后在-70℃下,一小时内加入72.7g液溴(反应物)的30ml二氯甲烷(溶剂)溶液,然后在-70℃下继续反应一小时,升温至0℃,将反应液倒入32%的160ml氢氧化钠水溶液(反应物)和300g冰中,通过滴加大约45g32%氢氧化钠水溶液来调节反应液的PH值至5~8。分液后水相用80ml二氯甲烷(溶剂)提取,合并有机相用4g硅藻土过滤,水洗,减压下蒸干溶剂。得到的粗产物柱层析后石油醚重结晶,得到23g产品,GC:99.9%。
MS:m/z%163(20.39)189(15.82)313(100)460(M+0.03)
1H-NMR:6.930~6.975(t,2H),6.829~6.866(d,2H),3.066~3.146(m,1H),2.516~2.542(m,2H),2.239~2.280(m,2H),2.059~2.099(m,2H),1.934~1.972(m,1H),1.325~1.334(m,6H),0.891~0.915(m,5H)
MP:41.5℃
由上可知,该产物结构正确,为式I所示化合物。
该化合物的液晶性能如下:
Δε:17.6(20℃,589nm)
实施例2、制备
本实施例的合成方法参照实施例1的7步反应,仅将步骤1中的溴代物3,5-二氟溴苯替换为3’,5’-二氟-4-溴联苯,产物依次向下投料反应,制备下述化合物。
其中,各步中间体分别为
步骤1
步骤2
步骤3
步骤4
步骤5
步骤6
步骤7
GC:99.93%
MS:m/z%239(2.77)252(3.41)265(9.94)389(100)536(M+0.66)
1H-NMR:7.472~7.499(d,2H),7.337~7.364(d,2H),7.179~7.256(d,2H),6.962~7.007(t,2H),3.109~3.231(m,1H),2.542~2.559(m,2H),2.291~2.333(m,2H),2.041~2.125(m,2H),1.902~1.997(m,1H),1.335~1.357(m,6H),0.885~0.920(m,5H)
MP:66.5℃
CP:40℃
由上可知,该产物结构正确,为式I所示化合物。其液晶性能检测结果如下:
Δε:14.3(20℃,589nm)
Δn:0.109(20℃,1000Hz)
实施例3、制备
步骤1
500ml三口瓶中加入31.2g实施例2中的得到的中间体(2-c)(反应物),200ml一缩二乙二醇(溶剂),60ml80%水合肼(反应物),加入氢氧化钾(催化剂)20g,一起加热回流发生黄鸣龙还原反应5小时,然后改为蒸馏。蒸出过量的水合肼至190-200℃,然后再回流3小时,降温至室温,倒入500ml水中,100ml×2(90-120)石油醚(溶剂)提取,水洗石油醚(溶剂)提取液至洗水中性,减压下蒸除石油醚(溶剂),残余物用石油醚(溶剂)重结晶,得到浅黄色固体17.8g(3-a),GC:99.1%。
步骤2
参照实施例1步骤6的合成方法,用27.3g(3-a)代替(1-e),得到18g(3-b),HPLC:98.8%
步骤3
参照实施例1步骤7的合成方法,用34.2g(3-b)代替(1-f),得到17g(3-c),
GC:99.92%。
MP:78℃
CP:6℃
该产物的结构检测结果与实施例1无实质性差别,此处不再赘述。
由上可知,该产物结构正确,为式I所示化合物。其液晶性能检测结果如下:
Δε:18(20℃,589nm)
Δn:0.121(20℃,1000Hz)
实施例4-29
使用实施例1-3所述方法,仅替换不同取代基对应的反应物,得到如下结构的式I所示液晶化合物:
其中,
的物化和液晶性能检测结果如下:
MP:63℃
CP:28℃
Δε:16(20℃,589nm)
Δn:0.129(20℃,1000Hz)
其中,的物化和液晶性能检测结果如下:
MP:67℃
CP:28℃
Δε:15(20℃,589nm)
Δn:0.094(20℃,1000Hz)
其中,的物化和液晶性能检测结果如下:
MP:70℃
CP:-12℃
Δε:17(20℃,589nm)
Δn:0.08(20℃,1000Hz)
其中,的物化和液晶性能检测结果如下:
MP:86℃
CP:76℃
Δε:10(20℃,589nm)
Δn:0.127(20℃,1000Hz)
上述实施例4-29所列其他式I所示化合物,其核磁检测结果和物化液晶性能检测结果与实施例1-3所得产物无实质性差别,不再赘述。
其中,如下结构的式I所示液晶化合物是按照实施例1所述方法,仅替换不同取代基对应的反应物而得,其余化合物按照实施例3所述方法仅替换不同取代基对应的反应物而得:
由上述实施例1-29可知,上述实施例制备所得式I所示液晶化合物具有良好的热稳定性和对紫外光的稳定性,适中的Δn,具有较大的正介电各向异性Δε,在光学器件中使用时可实现较低的阈值电压,同时还具有宽向列相范围和低旋转粘度γ1,对于实现显示器的快速响应具有重要意义,故非常适合用于调配液晶混合物。
实施例30、液晶混合物
将组分A和组分B以质量比为100∶13混匀,得到该实施例提供的液晶混合物。
其中,组分A中各组分名称及质量百分含量如下所示:
上述组分A的液晶性能检测结果如下:
清亮点[℃]:94.9
Δn[589nm,20℃]:0.119
Vth[V]:1.94
Δε[KHz,20℃]:5.3
组分B为实施例2制备所得式I所示化合物
该实施例所得液晶混合物的性能检测如下:
清亮点[℃]:91.6
Δn[589nm,20℃]:0.119
Vth[V]:1.74
Δε[KHz,20℃]:6.4
可知,式I所示化合物可降低液晶混合物的阈值电压。
实施例31、液晶混合物
将组分A和组分B混匀,得到液晶混合物。
其中,组分A中各组分名称及质量百分含量如下所示:
该组分A的液晶性能检测如下:
清亮点[℃]:74.6
Δn[589nm,20℃]:0.112
Vth[V]:1.95
Δε[KHz,20℃]:3.7
组分B为实施例2制备所得式I所示化合物实施例3制备所得和实施例17制备所得
其中,与组分A的质量比为6∶100;
与组分A的质量比为3∶100;
与组分A的质量比为4∶100。
该液晶混合物的性能检测如下:
清亮点[℃]:71.3
Δn[589nm,20℃]:0.114
Vth[V]:1.65
Δε[KHz,20℃]:4.8。
可知,式I所示化合物可降低液晶混合物的阈值电压。
工业应用
本发明提供的式I所示液晶化合物具有良好的热稳定性和对紫外光的稳定性,适中的Δn,具有较大的正介电各向异性Δε,在光学器件中使用具有较大的正介电各向异性Δε的混合物时可实现较低的阈值电压,同时还具有宽向列相范围,对于实现显示器的快速响应具有重要意义,故非常适合用于调配液晶混合物。故上述本发明提供的式I所示混合物或前述液晶混合物在制备液晶显示材料或电光学显示材料中的应用,以及包含上述本发明提供的式I所示混合物或前述液晶混合物中的至少一种的液晶显示材料或电光学液晶显示器,也属于本发明的保护范围。其中,所述显示器为TN-TFT显示器、STN显示器、IPS、VA显示器。
Claims (27)
1.式I1、式I5和式I11所示液晶化合物,
其中,所述式I1、式I5和式I11中,所述R11均选自氢、碳原子总数为1-10的直链烷基和碳原子总数为1-10的烷氧基中的至少一种,所述-(F)表示苯环上有氟原子取代基或氢。
2.包含组分A的液晶混合物;
所述组分A为权利要求1式I1、式I5和式I11所示液晶化合物中任意一种的液晶混合物。
3.根据权利要求2所述的液晶混合物,其特征在于:所述组分A中,所述式I1、式I5和式I11所示液晶化合物为1-5种。
4.根据权利要求3所述的液晶混合物,其特征在于:所述组分A中,所述式I1、式I5和式I11所示液晶化合物为1-3种。
5.根据权利要求2所述的液晶混合物,其特征在于:所述液晶混合物还包含组分B;
所述组分B为下述化合物式II-式XIV中的至少一种:
所述式II-式XI中,所述R3和R4均选自碳原子总数为1-9的正烷基、氟烷基、烷氧基、氧杂烷基、碳原子总数为2-9的链烯基和碳原子总数为2-9的链烯氧基中的至少一种;
所述Z均选自单键、-CH=CH-、-C≡C-、-COO-、-OOC-、-CF2O-、-CH2O-、-OCF2-、-CH2CH2-、-CF2CH2-、-C2F4-和-(CH2)4-中的至少一种;
Y均为H或F;
X均为F、Cl、碳原子总数为1-9的卤代烷基、碳原子总数为2-9的卤代链烯基、碳原子总数为2-9的链烯基、碳原子总数为1-9的卤代烷氧基、碳原子总数为2-9的卤代链烯基氧基和碳原子总数为1-9的烷基中的至少一种;
n均为0或1;
所述组分A与所述组分B的质量比为1-70:100。
6.根据权利要求5所述的液晶混合物,其特征在于:所述组分A与所述组分B的质量比为2-40:100。
7.根据权利要求6所述的液晶混合物,其特征在于:所述组分A与所述组分B的质量比为13:100。
8.根据权利要求7所述的液晶混合物,其特征在于:所述组分B为如下结构式的化合物中的至少一种:
9.根据权利要求2-8任一所述的液晶混合物,其特征在于:所述液晶混合物由所述组分A和所述组分B组成;
所述组分A与所述组分B的质量比为1-70:100。
10.根据权利要求9所述的液晶混合物,其特征在于:所述组分A与所述组分B的质量比为2-40:100。
11.根据权利要求10所述的液晶混合物,其特征在于:所述组分A与所述组分B的质量比为13:100。
12.根据权利要求2-8任一所述的液晶混合物,其特征在于:所述液晶混合物为如下组成的混合物a或b:
混合物a由组分A和组分B组成:
所述组分A为
所述组分B由如下质量比的各化合物组成:
其中,所述组分A与组分B的质量比为13:100;
混合物b由组分A和组分B组成:
所述组分A由 组成;
所述组分B由如下质量比的各化合物组成:
其中,所述组分A中,与组分B的质量比为6:100;
与组分B的质量比为3:100;
与组分B的质量比为4:100。
13.权利要求1所述液晶化合物或权利要求2-8任一所述液晶混合物在制备液晶显示材料或电光学显示材料中的应用。
14.权利要求9所述液晶混合物在制备液晶显示材料或电光学显示材料中的应用。
15.权利要求10所述液晶混合物在制备液晶显示材料或电光学显示材料中的应用。
16.权利要求11所述液晶混合物在制备液晶显示材料或电光学显示材料中的应用。
17.权利要求12所述液晶混合物在制备液晶显示材料或电光学显示材料中的应用。
18.包含权利要求1所述液晶化合物或权利要求2-8任一所述液晶混合物中的至少一种的液晶显示材料或电光学液晶显示器。
19.根据权利要求18所述的显示器,其特征在于:所述显示器为TN-TFT显示器、STN显示器、IPS显示器或VA显示器。
20.包含权利要求9所述液晶混合物中的至少一种的液晶显示材料或电光学液晶显示器。
21.根据权利要求20所述的显示器,其特征在于:所述显示器为TN-TFT显示器、STN显示器、IPS显示器或VA显示器。
22.包含权利要求10所述液晶混合物中的至少一种的液晶显示材料或电光学液晶显示器。
23.根据权利要求22所述的显示器,其特征在于:所述显示器为TN-TFT显示器、STN显示器、IPS显示器或VA显示器。
24.包含权利要求11所述液晶混合物中的至少一种的液晶显示材料或电光学液晶显示器。
25.根据权利要求24所述的显示器,其特征在于:所述显示器为TN-TFT显示器、STN显示器、IPS显示器或VA显示器。
26.包含权利要求12所述液晶混合物中的至少一种的液晶显示材料或电光学液晶显示器。
27.根据权利要求26所述的显示器,其特征在于:所述显示器为TN-TFT显示器、STN显示器、IPS显示器或VA显示器。
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JP6695727B2 (ja) * | 2016-04-08 | 2020-05-20 | 株式会社ジャパンディスプレイ | 表示装置 |
CN107118782A (zh) * | 2017-06-29 | 2017-09-01 | 石家庄诚志永华显示材料有限公司 | 一种液晶组合物 |
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CN103534335A (zh) | 2014-01-22 |
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