WO2013099754A1 - 2-フルオロフェニルオキシメタン構造を持つ化合物 - Google Patents
2-フルオロフェニルオキシメタン構造を持つ化合物 Download PDFInfo
- Publication number
- WO2013099754A1 WO2013099754A1 PCT/JP2012/083070 JP2012083070W WO2013099754A1 WO 2013099754 A1 WO2013099754 A1 WO 2013099754A1 JP 2012083070 W JP2012083070 W JP 2012083070W WO 2013099754 A1 WO2013099754 A1 WO 2013099754A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- general formula
- group
- atom
- compound
- compound represented
- Prior art date
Links
- 150000001875 compounds Chemical class 0.000 title claims abstract description 161
- JIXDOBAQOWOUPA-UHFFFAOYSA-N 1-fluoro-2-methoxybenzene Chemical group COC1=CC=CC=C1F JIXDOBAQOWOUPA-UHFFFAOYSA-N 0.000 title description 4
- 239000000203 mixture Substances 0.000 claims abstract description 76
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 74
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 64
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 43
- 238000004519 manufacturing process Methods 0.000 claims abstract description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 37
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 32
- 125000001309 chloro group Chemical group Cl* 0.000 claims abstract description 32
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 28
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 15
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 8
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 59
- -1 borate ester Chemical class 0.000 claims description 58
- 125000004432 carbon atom Chemical group C* 0.000 claims description 44
- 229910052727 yttrium Inorganic materials 0.000 claims description 33
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 30
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 28
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 28
- 229910052740 iodine Inorganic materials 0.000 claims description 28
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 239000003054 catalyst Substances 0.000 claims description 23
- 239000002585 base Substances 0.000 claims description 22
- 229910052723 transition metal Inorganic materials 0.000 claims description 22
- 150000003624 transition metals Chemical class 0.000 claims description 22
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- 125000005951 trifluoromethanesulfonyloxy group Chemical group 0.000 claims description 13
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 125000005905 mesyloxy group Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 claims description 7
- 238000006266 etherification reaction Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical class OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 claims description 5
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 229910001860 alkaline earth metal hydroxide Inorganic materials 0.000 claims description 2
- 125000005603 azodicarboxylic group Chemical group 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 claims 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims 1
- 150000008041 alkali metal carbonates Chemical class 0.000 claims 1
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims 1
- 150000001342 alkaline earth metals Chemical class 0.000 claims 1
- 150000002736 metal compounds Chemical class 0.000 claims 1
- 125000001979 organolithium group Chemical group 0.000 claims 1
- 150000003003 phosphines Chemical class 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 78
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 63
- 239000002904 solvent Substances 0.000 description 62
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 60
- 239000012044 organic layer Substances 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 33
- 239000000243 solution Substances 0.000 description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 20
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 19
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 19
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 description 17
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 16
- 229910052938 sodium sulfate Inorganic materials 0.000 description 16
- 235000011152 sodium sulphate Nutrition 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- 230000001965 increasing effect Effects 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 15
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 15
- 229910001868 water Inorganic materials 0.000 description 15
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 14
- 238000013213 extrapolation Methods 0.000 description 13
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 238000010898 silica gel chromatography Methods 0.000 description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 11
- 238000010992 reflux Methods 0.000 description 11
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 10
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- 0 *c(cc1*)cc(cc2*)c1c(*)c2F Chemical compound *c(cc1*)cc(cc2*)c1c(*)c2F 0.000 description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 9
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 9
- 239000004210 ether based solvent Substances 0.000 description 8
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 8
- 238000000605 extraction Methods 0.000 description 8
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 150000001408 amides Chemical class 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 125000005647 linker group Chemical group 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- ILQZCTDZLUKETN-UHFFFAOYSA-N 2,6-difluoro-4-propylphenol Chemical compound CCCC1=CC(F)=C(O)C(F)=C1 ILQZCTDZLUKETN-UHFFFAOYSA-N 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 125000003545 alkoxy group Chemical group 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 6
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000007704 transition Effects 0.000 description 6
- NEXJIGWPQFTBCS-UHFFFAOYSA-N 2-[(4-bromophenyl)methoxy]-1,3-difluoro-5-propylbenzene Chemical compound CCCc1cc(F)c(OCc2ccc(Br)cc2)c(F)c1 NEXJIGWPQFTBCS-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- LXNAVEXFUKBNMK-UHFFFAOYSA-N palladium(II) acetate Substances [Pd].CC(O)=O.CC(O)=O LXNAVEXFUKBNMK-UHFFFAOYSA-N 0.000 description 5
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical class OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 5
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 description 5
- USVVENVKYJZFMW-ONEGZZNKSA-N (e)-carboxyiminocarbamic acid Chemical compound OC(=O)\N=N\C(O)=O USVVENVKYJZFMW-ONEGZZNKSA-N 0.000 description 4
- KZPYGQFFRCFCPP-UHFFFAOYSA-N 1,1'-bis(diphenylphosphino)ferrocene Chemical compound [Fe+2].C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=C[C-]1P(C=1C=CC=CC=1)C1=CC=CC=C1 KZPYGQFFRCFCPP-UHFFFAOYSA-N 0.000 description 4
- XXJLEFLAVIIDIH-UHFFFAOYSA-N 1,2,3-trifluoro-6-[2-fluoro-4-(4-propylphenyl)phenyl]naphthalene Chemical compound CCCc1ccc(cc1)-c1ccc(c(F)c1)-c1ccc2c(F)c(F)c(F)cc2c1 XXJLEFLAVIIDIH-UHFFFAOYSA-N 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000007818 Grignard reagent Substances 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000001298 alcohols Chemical class 0.000 description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 4
- 239000004327 boric acid Substances 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
- 229910000024 caesium carbonate Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- NXQGGXCHGDYOHB-UHFFFAOYSA-L cyclopenta-1,4-dien-1-yl(diphenyl)phosphane;dichloropalladium;iron(2+) Chemical compound [Fe+2].Cl[Pd]Cl.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1.[CH-]1C=CC(P(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 NXQGGXCHGDYOHB-UHFFFAOYSA-L 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- YNHIGQDRGKUECZ-UHFFFAOYSA-N dichloropalladium;triphenylphosphanium Chemical compound Cl[Pd]Cl.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1[PH+](C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 150000002334 glycols Chemical class 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
- VVWRJUBEIPHGQF-MDZDMXLPSA-N propan-2-yl (ne)-n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)\N=N\C(=O)OC(C)C VVWRJUBEIPHGQF-MDZDMXLPSA-N 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- LMWULDAKYOYQRI-UHFFFAOYSA-N 4-(3,5-difluorophenyl)cyclohexane-1-carbaldehyde Chemical compound FC1=CC(F)=CC(C2CCC(CC2)C=O)=C1 LMWULDAKYOYQRI-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- 239000004988 Nematic liquid crystal Substances 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000543 intermediate Substances 0.000 description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 150000002902 organometallic compounds Chemical class 0.000 description 3
- IVDFJHOHABJVEH-UHFFFAOYSA-N pinacol Chemical compound CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- VVWRJUBEIPHGQF-UHFFFAOYSA-N propan-2-yl n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)N=NC(=O)OC(C)C VVWRJUBEIPHGQF-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- FMPAMLJNPAFHSV-UHFFFAOYSA-N 1,2-difluoro-6-[4-[(2-fluoro-4-methylphenoxy)methyl]phenyl]naphthalene Chemical compound Cc1ccc(OCc2ccc(cc2)-c2ccc3c(F)c(F)ccc3c2)c(F)c1 FMPAMLJNPAFHSV-UHFFFAOYSA-N 0.000 description 2
- GHOUEKQRKXYGHJ-UHFFFAOYSA-N 1,3-difluoro-5-(4-propylcyclohexyl)benzene Chemical compound C1CC(CCC)CCC1C1=CC(F)=CC(F)=C1 GHOUEKQRKXYGHJ-UHFFFAOYSA-N 0.000 description 2
- VHWBOTFVHSCYJC-UHFFFAOYSA-N 1-(3,5-difluorophenyl)-4-propylcyclohexan-1-ol Chemical compound C1CC(CCC)CCC1(O)C1=CC(F)=CC(F)=C1 VHWBOTFVHSCYJC-UHFFFAOYSA-N 0.000 description 2
- KLBRTJRNQIUKHJ-UHFFFAOYSA-N 1-[(4-bromophenyl)methoxy]-2-fluoro-4-methylbenzene Chemical compound Cc1ccc(OCc2ccc(Br)cc2)c(F)c1 KLBRTJRNQIUKHJ-UHFFFAOYSA-N 0.000 description 2
- OMJIWSOTOGVPTA-UHFFFAOYSA-N 2-[(3,5-difluorophenyl)methoxy]-1,3-difluoro-5-propylbenzene Chemical compound CCCc1cc(F)c(OCc2cc(F)cc(F)c2)c(F)c1 OMJIWSOTOGVPTA-UHFFFAOYSA-N 0.000 description 2
- MIKIIGOGUULCIT-UHFFFAOYSA-N 5,6,7-trifluoronaphthalen-2-ol Chemical compound FC1=C(F)C(F)=CC2=CC(O)=CC=C21 MIKIIGOGUULCIT-UHFFFAOYSA-N 0.000 description 2
- XKYCQXHOHPKAFN-XYWHTSSQSA-N CCC[C@H]1CC[C@@H](CC1)c1cc(F)c(OCc2ccc(cc2)-c2ccc3c(F)c(F)c(F)cc3c2)c(F)c1 Chemical compound CCC[C@H]1CC[C@@H](CC1)c1cc(F)c(OCc2ccc(cc2)-c2ccc3c(F)c(F)c(F)cc3c2)c(F)c1 XKYCQXHOHPKAFN-XYWHTSSQSA-N 0.000 description 2
- GPMLFKYXJYGRNI-CTYIDZIISA-N CCCc1cc(F)c(OC[C@H]2CC[C@@H](CC2)c2cc(F)c(OB(O)O)c(F)c2)c(F)c1 Chemical compound CCCc1cc(F)c(OC[C@H]2CC[C@@H](CC2)c2cc(F)c(OB(O)O)c(F)c2)c(F)c1 GPMLFKYXJYGRNI-CTYIDZIISA-N 0.000 description 2
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QDSYNNDNKIIHTN-UHFFFAOYSA-N [4-[(2,6-difluoro-4-propylphenoxy)methyl]-2,6-difluorophenoxy]boronic acid Chemical compound CCCc1cc(F)c(OCc2cc(F)c(OB(O)O)c(F)c2)c(F)c1 QDSYNNDNKIIHTN-UHFFFAOYSA-N 0.000 description 2
- WQOCCVHIJIGIQO-UHFFFAOYSA-N [4-[(2,6-difluoro-4-propylphenoxy)methyl]phenoxy]boronic acid Chemical compound CCCc1cc(F)c(OCc2ccc(OB(O)O)cc2)c(F)c1 WQOCCVHIJIGIQO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000005453 ketone based solvent Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 2
- WJKHJLXJJJATHN-UHFFFAOYSA-N triflic anhydride Chemical compound FC(F)(F)S(=O)(=O)OS(=O)(=O)C(F)(F)F WJKHJLXJJJATHN-UHFFFAOYSA-N 0.000 description 2
- GNUFQJQCEBFWDQ-UHFFFAOYSA-N (3,5-difluorophenoxy)boronic acid Chemical compound OB(O)OC1=CC(F)=CC(F)=C1 GNUFQJQCEBFWDQ-UHFFFAOYSA-N 0.000 description 1
- LOGIHEKXJKHXEC-UHFFFAOYSA-N (3,5-difluorophenyl)methanol Chemical compound OCC1=CC(F)=CC(F)=C1 LOGIHEKXJKHXEC-UHFFFAOYSA-N 0.000 description 1
- KKMGCMNVSQLLCF-UHFFFAOYSA-N (5,6-difluoronaphthalen-2-yl) trifluoromethanesulfonate Chemical compound C1=C(OS(=O)(=O)C(F)(F)F)C=CC2=C(F)C(F)=CC=C21 KKMGCMNVSQLLCF-UHFFFAOYSA-N 0.000 description 1
- DSLKOTQBUFGMQY-UHFFFAOYSA-N 1,2,3-trifluoronaphthalene Chemical compound C1=CC=C2C(F)=C(F)C(F)=CC2=C1 DSLKOTQBUFGMQY-UHFFFAOYSA-N 0.000 description 1
- NONGEOXDYYYIJI-UHFFFAOYSA-N 1,3-difluoro-2-methoxy-5-propylbenzene Chemical compound CCCC1=CC(F)=C(OC)C(F)=C1 NONGEOXDYYYIJI-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
- YLRBJYMANQKEAW-UHFFFAOYSA-N 1-bromo-4-(bromomethyl)benzene Chemical compound BrCC1=CC=C(Br)C=C1 YLRBJYMANQKEAW-UHFFFAOYSA-N 0.000 description 1
- YFBUGJCKJRLVMM-UHFFFAOYSA-N 1-fluoro-3-(3-fluoropropyl)benzene Chemical compound FCCCC1=CC=CC(F)=C1 YFBUGJCKJRLVMM-UHFFFAOYSA-N 0.000 description 1
- WZFUQSJFWNHZHM-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)N1CC2=C(CC1)NN=N2 WZFUQSJFWNHZHM-UHFFFAOYSA-N 0.000 description 1
- WJKISRFVKIOBCQ-UHFFFAOYSA-N 2-fluoro-4-methylphenol Chemical compound CC1=CC=C(O)C(F)=C1 WJKISRFVKIOBCQ-UHFFFAOYSA-N 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- DTBDAFLSBDGPEA-UHFFFAOYSA-N 3-Methylquinoline Natural products C1=CC=CC2=CC(C)=CN=C21 DTBDAFLSBDGPEA-UHFFFAOYSA-N 0.000 description 1
- NQEDLIZOPMNZMC-UHFFFAOYSA-N 4-propylcyclohexan-1-one Chemical compound CCCC1CCC(=O)CC1 NQEDLIZOPMNZMC-UHFFFAOYSA-N 0.000 description 1
- REURAJIXHRFHNH-UHFFFAOYSA-N 5,6-difluoronaphthalen-2-ol Chemical compound FC1=C(F)C=CC2=CC(O)=CC=C21 REURAJIXHRFHNH-UHFFFAOYSA-N 0.000 description 1
- ANKYSFYOCCHJFG-UHFFFAOYSA-N 5-[[4-(3,5-difluorophenyl)phenyl]methyl]-1,3-difluoro-2-propylbenzene Chemical compound CCCc1c(F)cc(Cc2ccc(cc2)-c2cc(F)cc(F)c2)cc1F ANKYSFYOCCHJFG-UHFFFAOYSA-N 0.000 description 1
- NGSQAWUNHYKIQG-UHFFFAOYSA-N 6-[4-[(2,6-difluoro-4-propylphenoxy)methyl]-2,6-difluorophenyl]-1,2,3-trifluoronaphthalene Chemical compound CCCc1cc(F)c(OCc2cc(F)c(c(F)c2)-c2ccc3c(F)c(F)c(F)cc3c2)c(F)c1 NGSQAWUNHYKIQG-UHFFFAOYSA-N 0.000 description 1
- XRGUSANMWCXHEX-UHFFFAOYSA-N 6-[4-[(2,6-difluoro-4-propylphenoxy)methyl]phenyl]-1,2,3-trifluoronaphthalene Chemical compound CCCc1cc(F)c(OCc2ccc(cc2)-c2ccc3c(F)c(F)c(F)cc3c2)c(F)c1 XRGUSANMWCXHEX-UHFFFAOYSA-N 0.000 description 1
- BMBAKXSIGUNXAX-UHFFFAOYSA-N 6-[4-[4-[(2,6-difluoro-4-propylphenoxy)methyl]phenyl]-2,6-difluorophenyl]-1,2,3-trifluoronaphthalene Chemical compound CCCc1cc(F)c(OCc2ccc(cc2)-c2cc(F)c(c(F)c2)-c2ccc3c(F)c(F)c(F)cc3c2)c(F)c1 BMBAKXSIGUNXAX-UHFFFAOYSA-N 0.000 description 1
- KVWADYROGPVRLB-UHFFFAOYSA-N C(C)(C)(C)[Li].C(C)(C)(C)[Li] Chemical compound C(C)(C)(C)[Li].C(C)(C)(C)[Li] KVWADYROGPVRLB-UHFFFAOYSA-N 0.000 description 1
- FIIWXUSCJAYKEP-UHFFFAOYSA-N CC(c(c(C1CC1)cc(-c1ccccc1)c1)c1F)=C Chemical compound CC(c(c(C1CC1)cc(-c1ccccc1)c1)c1F)=C FIIWXUSCJAYKEP-UHFFFAOYSA-N 0.000 description 1
- ZEFUVKDPLIHRSI-XYPYZODXSA-N CCC[C@H]1CC[C@@H](CC1)c1cc(F)c(O)c(F)c1 Chemical compound CCC[C@H]1CC[C@@H](CC1)c1cc(F)c(O)c(F)c1 ZEFUVKDPLIHRSI-XYPYZODXSA-N 0.000 description 1
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- QPGLVYDFVJFIOT-MGCOHNPYSA-N OC[C@H]1CC[C@@H](CC1)c1cc(F)cc(F)c1 Chemical compound OC[C@H]1CC[C@@H](CC1)c1cc(F)cc(F)c1 QPGLVYDFVJFIOT-MGCOHNPYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 241000219289 Silene Species 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- QPGLVYDFVJFIOT-UHFFFAOYSA-N [4-(3,5-difluorophenyl)cyclohexyl]methanol Chemical compound C1CC(CO)CCC1C1=CC(F)=CC(F)=C1 QPGLVYDFVJFIOT-UHFFFAOYSA-N 0.000 description 1
- TXLWYOSMKCXNND-UHFFFAOYSA-N [4-[(2-fluoro-4-methylphenoxy)methyl]phenyl]boronic acid Chemical compound Cc1ccc(OCc2ccc(cc2)B(O)O)c(F)c1 TXLWYOSMKCXNND-UHFFFAOYSA-N 0.000 description 1
- GYAVCFZYFMMHEA-UHFFFAOYSA-N [Li]C(C)CC.[Li]C(C)CC Chemical compound [Li]C(C)CC.[Li]C(C)CC GYAVCFZYFMMHEA-UHFFFAOYSA-N 0.000 description 1
- HIJMOEODDGNLNS-UHFFFAOYSA-N [Li]CCCC.[Li]CCCC Chemical compound [Li]CCCC.[Li]CCCC HIJMOEODDGNLNS-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 150000003973 alkyl amines Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000000470 constituent Substances 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
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- FAMRKDQNMBBFBR-BQYQJAHWSA-N diethyl azodicarboxylate Substances CCOC(=O)\N=N\C(=O)OCC FAMRKDQNMBBFBR-BQYQJAHWSA-N 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 229940043279 diisopropylamine Drugs 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- FAMRKDQNMBBFBR-UHFFFAOYSA-N ethyl n-ethoxycarbonyliminocarbamate Chemical compound CCOC(=O)N=NC(=O)OCC FAMRKDQNMBBFBR-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- AFRJJFRNGGLMDW-UHFFFAOYSA-N lithium amide Chemical class [Li+].[NH2-] AFRJJFRNGGLMDW-UHFFFAOYSA-N 0.000 description 1
- NVMMPHVQFFIBOS-UHFFFAOYSA-N lithium;dibutylazanide Chemical compound [Li+].CCCC[N-]CCCC NVMMPHVQFFIBOS-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- CZFNISFYDPIDNM-UHFFFAOYSA-N n,n-dimethylformamide;oxolane Chemical compound CN(C)C=O.C1CCOC1 CZFNISFYDPIDNM-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- VEDDBHYQWFOITD-UHFFFAOYSA-N para-bromobenzyl alcohol Chemical compound OCC1=CC=C(Br)C=C1 VEDDBHYQWFOITD-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- XPPWLXNXHSNMKC-UHFFFAOYSA-N phenylboron Chemical compound [B]C1=CC=CC=C1 XPPWLXNXHSNMKC-UHFFFAOYSA-N 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000005651 substituted 1,4-phenylene group Chemical group 0.000 description 1
- 125000001412 tetrahydropyranyl group Chemical group 0.000 description 1
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
Classifications
-
- 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
- C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
- C07C41/30—Preparation of ethers by reactions not forming ether-oxygen bonds by increasing the number of carbon atoms, e.g. by oligomerisation
-
- 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
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
-
- 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
- C09K19/062—Non-steroidal liquid crystal compounds containing one non-condensed benzene ring
-
- 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
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/32—Non-steroidal liquid crystal compounds containing condensed ring systems, i.e. fused, bridged or spiro ring systems
- C09K19/322—Compounds containing a naphthalene ring or a completely or partially hydrogenated naphthalene ring
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K19/00—Liquid crystal materials
- C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
- C09K19/06—Non-steroidal liquid crystal compounds
- C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
-
- 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
- C09K19/40—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals
- C09K19/404—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen or sulfur, e.g. silicon, metals containing boron or phosphorus
-
- 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
-
- 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
Definitions
- the present invention relates to a compound having a 2-fluorophenyloxymethane structure, which is useful as an organic electronic material or medical pesticide, particularly as a material for a liquid crystal display element.
- Liquid crystal display elements are used in various measuring instruments, automobile panels, word processors, electronic notebooks, printers, computers, televisions, clocks, advertisement display boards, etc., including watches and calculators.
- Typical liquid crystal display methods include TN (twisted nematic) type, STN (super twisted nematic) type, vertical alignment type using TFT (thin film transistor), and IPS (in-plane switching) type.
- Etc The liquid crystal compositions used in these liquid crystal display elements are stable against external factors such as moisture, air, heat, and light, and the liquid crystal phase (nematic phase, smectic phase) in the widest possible temperature range centering on room temperature. Phase, blue phase, etc.), low viscosity, and low driving voltage. Further, the liquid crystal composition must have optimum values of dielectric anisotropy ( ⁇ ), refractive index anisotropy ( ⁇ n) and the like in accordance with individual display elements.
- ⁇ dielectric anisotropy
- ⁇ n refractive index
- a liquid crystal composition having a positive ⁇ is used in a horizontal alignment type display such as a TN type, STN type, or IPS type.
- a driving method has been reported in which a liquid crystal composition having a positive ⁇ is vertically aligned when no voltage is applied and a lateral electric field is applied to display the liquid crystal composition. Yes.
- an improvement in response speed is required in all driving systems, and in order to solve this problem, a liquid crystal composition having a viscosity lower than that of the present is required.
- it is effective to reduce the viscosity of the individual compounds constituting the liquid crystal composition.
- it is calculated
- the molecular skeleton has a structure in which a plurality of ring structures are directly bonded without a linking group, that is, a so-called straight ring structure.
- the value of ⁇ is positive, and compounds having a straight ring structure composed of three or more ring structures generally have high crystallinity, and crystals of the compound are precipitated when the liquid crystal composition containing the compound is cooled.
- a compound having the following fluorinated naphthalene structure see Patent Document 1
- JP 2000-355560 A JP 10-101599 A 2 to 501111 JP-A-9-157202 Special table 2005-517079 JP-A-2-233626 4-501575 Special table flat 6-504032 WO98 / 23564
- the problem to be solved by the present invention is to provide a compound having a low viscosity ( ⁇ ) and high miscibility with other liquid crystal compounds and a method for producing the same, and a liquid crystal composition and a liquid crystal comprising the compound as a constituent member It is to provide a display element.
- the present inventors have studied various compounds, and as a result, found that a compound having a 2-fluorophenyloxymethane structure can effectively solve the problems, and further efficiently used the compounds of the present application. Intermediates effective for synthesis and methods for producing them were studied, and the present invention was completed.
- R 1 represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one —CH 2 — or two non-adjacent groups present in these groups.
- the above -CH 2 - may be independently replaced by -O-, -S-, -COO-, -OCO- or -CO-
- a 1 represents (a) a 1,4-cyclohexylene group (one —CH 2 — present in this group or two or more non-adjacent —CH 2 — are each independently O— or — (It may be replaced by S-)
- B 1,4-phenylene group (one —CH ⁇ present in this group or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ , present in this group)
- the hydrogen atom to be substituted may be replaced by a fluorine atom.
- a group selected from the group consisting of: Z 1 is —CH 2 O—,
- a 2 represents the same meaning as A 1 in the general formula (2)
- a 3 represents a 1,4-phenylene group (a hydrogen atom present in this group may be substituted with a fluorine atom)
- X 1 represents a hydroxy group, a chlorine atom, a bromine atom, an iodine atom, a tosyloxy group, a mesyloxy group or a trifluoromethanesulfonyloxy group
- X 2 represents a chlorine atom, a bromine atom or an iodine atom
- a 3 is (A-1) or (A-2)
- a hydrogen atom when it is a group selected from Z 2 represents the same meaning as Z 1 in the general formula (2), n represents 0 or 1.
- an etherification reaction is carried out in the presence of a base.
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 4 and X 2 are each independently R in General Formula (2) or General Formula (3)).
- 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 4 and X 2 are represented by the same formula), and represented by the general formula (4)
- the compound of formula (5) is prepared by reacting the compound to be reacted with a metal or an organic metal, or substituting the metal of the obtained organometallic compound with another atom.
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n and Y 4 are each independently R 1 , A 1 , A 2 , A in General Formula (4). 3 , Z 1 , Z 2 , m, n and Y 4 represent the same meaning, X 3 represents MgX 4 , Li, ZnX 4 , CuX 4 (wherein X 4 represents a chlorine atom, a bromine atom or an iodine atom), or a general formula (B-1) or (B-2)
- R 2 and R 3 each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms
- E represents — (CH 2 ) p — in which one or more hydrogen atoms present in the group may each independently be substituted with a methyl group; p represents 2, 3 or 4.
- Y 1 , Y 2 and Y 3 each independently represents a hydrogen atom, a fluorine atom or a chlorine atom, X 5 represents a trifluoromethanesulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom.
- a transition metal catalyst (1)
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 1 , Y 2 , Y 3 and Y 4 are each independently represented by General Formula (5) and General It represents the same meaning as R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 1 , Y 2 , Y 3 and Y 4 in Formula (6)).
- compound that can be produced is produced.
- a liquid crystal composition containing the compound and a liquid crystal display element using the liquid crystal composition are provided.
- the compound represented by the general formula (1) provided by the present invention can be industrially efficiently produced through the compounds represented by the general formula (4) and the general formula (5).
- the obtained compound represented by the general formula (1) has both a low viscosity and a high miscibility with other liquid crystal compounds.
- a liquid crystal composition exhibiting a liquid crystal phase with a low viscosity and a wide temperature range can be obtained at low cost. For this reason, it is very useful as a component of a liquid crystal composition for a liquid crystal display element that requires a high-speed response.
- R 1 represents an alkyl group having 1 to 15 carbon atoms or an alkenyl group having 2 to 15 carbon atoms, and one —CH 2 — or two non-adjacent groups present in these groups.
- the above -CH 2 - may be independently replaced by -O-, -S-, -COO-, -OCO- or -CO-
- a 1 represents (a) a 1,4-cyclohexylene group (one —CH 2 — present in this group or two or more non-adjacent —CH 2 — are each independently O— or — it may be replaced by the S-.)
- B 1,4-phenylene group (one —CH ⁇ present in this group or two or more non-adjacent —CH ⁇ may be replaced by —N ⁇ , present in this group)
- the hydrogen atom to be substituted may be replaced by a fluorine atom.
- a group selected from the group consisting of: Z 1 is —CH 2 O—,
- a 2 represents the same meaning as A 1 in the general formula (2)
- a 3 represents a 1,4-phenylene group (a hydrogen atom present in this group may be substituted with a fluorine atom)
- X 1 represents a hydroxy group, a chlorine atom, a bromine atom, an iodine atom, a tosyloxy group, a mesyloxy group or a trifluoromethanesulfonyloxy group
- X 2 represents a chlorine atom, a bromine atom or an iodine atom
- a 3 is (A-1) or (A-2)
- a hydrogen atom when it is a group selected from Z 2 represents the same meaning as Z 1 in the general formula (2), n represents 0 or 1.
- an etherification reaction is carried out in the presence of a base.
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 4 and X 2 are each independently R in General Formula (2) or General Formula (3)).
- X 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 4, and X 2 are each independently R in General Formula (2) or General Formula (3).
- X 1 is preferably a bromine atom, an iodine atom or a mesyloxy group.
- X 2 is preferably a hydrogen atom, a bromine atom or an iodine atom.
- the compound represented by the general formula (4) is reacted with a metal or an organic metal, or the metal of the obtained organometallic compound is further substituted with another atom, and the general formula (5)
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n and Y 4 are each independently R 1 , A 1 , A 2 , A in General Formula (4). 3 , Z 1 , Z 2 , m, n and Y 4 represent the same meaning, X 3 represents MgX 4 , Li, Na, ZnX 4 or CuX 4 (wherein X 4 represents a chlorine atom, a bromine atom or an iodine atom) or a general formula (B-1) or (B-2)
- R 2 and R 3 each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms
- E represents — (CH 2 ) p — in which one or more hydrogen atoms present in the group may each independently be substituted with a methyl group; p represents 2, 3 or 4.
- X 3 is MgX 4 or ZnX 4 in which X 4 is a bromine atom or a chlorine atom, or General Formula (B-1) in which R 2 and R 3 are hydrogen atoms or The general formula (B-2) in which p is 2 or 3 is preferable.
- Y 1 , Y 2 and Y 3 each independently represents a hydrogen atom, a fluorine atom or a chlorine atom, X 5 represents a trifluoromethanesulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom.
- a transition metal catalyst (1)
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 1 , Y 2 , Y 3 and Y 4 are each independently represented by General Formula (5) and General It represents the same meaning as R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 1 , Y 2 , Y 3 and Y 4 in Formula (6)).
- X 5 is preferably a trifluoromethanesulfonyloxy group, an iodine atom or a bromine atom.
- R is preferably an alkyl group having 1 to 8 carbon atoms or an alkenyl group having 2 to 8 carbon atoms in order to reduce the viscosity, and alkyl having 1 to 5 carbon atoms.
- a group or an alkenyl group having 2 to 5 carbon atoms is particularly preferred. Moreover, it is preferable that it is linear.
- a 1 and A 2 are each independently preferably a trans-1,4-cyclohexylene group or an unsubstituted 1,4-phenylene group for decreasing the viscosity, and trans-1,4-cyclohexyl group is preferable.
- trans-1,4-cyclohexyl group is preferable.
- it is more preferable that it is a silene group.
- a 1,4-phenylene group which is not substituted with a fluorine atom is preferable, and in order to improve solubility,
- Z 1 and Z 2 are each independently —CH 2 O—, —OCH 2 —, —CF 2 O—, —OCF 2 —, —CF ⁇ CF— or a single bond for decreasing the viscosity. It is preferably a —CF 2 O—, —OCF 2 —, —CH 2 O—, —OCH 2 — or a single bond.
- Y 4 is preferably a hydrogen atom or a fluorine atom for decreasing the viscosity, preferably a fluorine atom for increasing ⁇ , and may be a fluorine atom for improving the solubility. preferable.
- Y 1 , Y 2 and Y 3 are each independently preferably a hydrogen atom for decreasing the viscosity, and at least two are preferably fluorine atoms for increasing ⁇ . Are preferably fluorine atoms. In order to improve the solubility, at least one is preferably a hydrogen atom, and more preferably all three are hydrogen atoms.
- M is preferably 0 when importance is attached to viscosity, preferably 1 for increasing ⁇ , and preferably 0 for improving solubility.
- n is preferably 0 when importance is attached to viscosity, preferably 1 for increasing ⁇ , and preferably 0 for improving solubility.
- each R 1 independently represents an alkyl group having 1 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, an alkoxy group having 1 to 15 carbon atoms, or an alkenyloxy group having 2 to 15 carbon atoms.
- the lower limit value in the liquid crystal composition is 1% (% in the composition is% by mass).
- the upper limit is preferably 50%, more preferably 30%, still more preferably 20%, and particularly preferably 10%.
- the compound represented by General formula (1) can also be used by 1 type, you may use 2 or more types of compounds simultaneously.
- a compound other than the compound represented by the general formula (1) may be used.
- a compound having a liquid crystal phase a compound having no liquid crystal phase may be used as necessary. It can also be added.
- the general component (1) At least one compound represented by the formula (2), but it is preferable to contain at least one of the following second to sixth components as other components.
- the second component is a so-called fluorine-based (halogen-based) p-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (A1) to (A3).
- R b represents an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and has a 3- to 6-membered cyclic structure. Any —CH 2 — present in the group may be replaced by —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, 2 to A linear 1-alkenyl group having 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms at the end.
- the compound may be optically active or racemic.
- Ring A, Ring B and Ring C may each independently be substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms.
- An optional naphthalene-2,6-diyl group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms is preferred.
- ring A when ring B is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring A may be a trans-1,4-cyclohexylene group.
- ring C when ring C is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring B and ring A are trans-1,4-cyclohexylene groups.
- ring A3 is preferably a trans-1,4-cyclohexylene group.
- L a , L b and L c are each a linking group and each independently represents a single bond, an ethylene group (—CH 2 CH 2 —), a 1,2-propylene group (—CH (CH 3 ) CH 2 — and —CH 2 CH (CH 3 ) —), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, — CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C— or —CH ⁇ NN ⁇ CH—, each represents a single bond, ethylene group, 1,4-butylene group, —COO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF— or —C ⁇ C— is preferable, and a single bond or an ethylene group is particularly preferable. Further, it is preferable that at least one of (A2) represents a single bond and at least two of (A3) represent
- Ring Z is an aromatic ring and represents any one of the following general formulas (La) to (Lc).
- Y a to Y j each independently represent a hydrogen atom or a fluorine atom.
- at least one of Y a and Y b is preferably a fluorine atom
- at least one of Y d to Y f is preferably a fluorine atom, more preferably Y d is more preferably a fluorine atom
- at least one of Y h and Y i is a fluorine atom
- Y h is more preferably a fluorine atom.
- Terminal group P a represents a fluorine atom, a chlorine atom, trifluoromethoxy group, difluoromethoxy group, trifluoromethyl group or difluoromethyl group, two or more carbon atoms substituted by fluorine atoms 2 or 3 alkoxy groups, 2 An alkyl group having 2 or 3 carbon atoms substituted by 2 or more fluorine atoms, an alkenyl group having 2 or 3 carbon atoms substituted by 2 or more fluorine atoms, or a carbon substituted by 2 or more fluorine atoms Although an alkenyloxy group having 2 or 3 atoms is represented, a fluorine atom, a trifluoromethoxy group or a difluoromethoxy group is preferable, and a fluorine atom is particularly preferable.
- the third component is a so-called cyano p-type liquid crystal compound, and examples thereof include compounds represented by the following general formulas (B1) to (B3).
- R c represents an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and has a 3- to 6-membered cyclic structure. Any —CH 2 — present in the group may be replaced by —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or —C ⁇ C—.
- Any hydrogen atom present in the group may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl group having 1 to 7 carbon atoms, 2 to A linear 1-alkenyl group having 7 carbon atoms, a linear 3-alkenyl group having 4 to 7 carbon atoms, and an alkyl group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 3 carbon atoms at the end.
- the compound may be optically active or racemic.
- Ring D, Ring E and Ring F may each independently be substituted with a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, or one or more fluorine atoms.
- the good naphthalene-2,6-diyl group or 1 to 2 fluorine atoms also may be substituted 1,4-phenylene group is preferred.
- ring D when ring E is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group, ring D may be a trans-1,4-cyclohexylene group.
- Ring F is a trans-1,4-cyclohexylene group or a transdecahydronaphthalene-trans-2,6-diyl group
- Ring D and Ring E are trans-1,4-cyclohexylene groups.
- ring D is preferably a trans-1,4-cyclohexylene group.
- L d , L e and L f are each a linking group and each independently represents a single bond, an ethylene group (—CH 2 CH 2 —), a 1,2-propylene group (—CH (CH 3 ) CH 2 — and ) —CH 2 CH (CH 3 ) —), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C—, —OCH 2 —, —CH 2 O— or —CH ⁇ NN ⁇ CH— represents a single bond, an ethylene group, —COO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF— or —C ⁇ C— are preferred, and a single bond, an ethylene group or —COO— is particularly preferred.
- at least one of them preferably represents a
- P b represents a cyano group
- Ring Y is an aromatic ring and represents any one of the following general formulas (Ld) to (Lf).
- Y k to Y q each independently represent a hydrogen atom or a fluorine atom.
- at least one of Y k and Y l is preferably a fluorine atom
- Y m to Y o are preferably fluorine atoms, particularly Y m is more preferably a fluorine atom
- at least one of Y p and Y q is a fluorine atom.
- Y p is a fluorine atom.
- the fourth component is a so-called nonpolar liquid crystal compound having a dielectric anisotropy of about 0, and examples thereof include compounds represented by the following general formulas (C1) to (C3).
- R d and Pe each independently represent an alkyl group having 1 to 12 carbon atoms, which may be linear or branched, and may be a 3- to 6-membered ring
- Any —CH 2 — that may have a cyclic structure and is present in the group is —O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF— or Any hydrogen atom present in the group may be substituted by —C ⁇ C— and may be substituted by a fluorine atom or a trifluoromethoxy group, but a linear alkyl having 1 to 7 carbon atoms A straight-chain 1-alkenyl group having 2 to 7 carbon atoms, a straight-chain 3-alkenyl group having 4 to 7 carbon atoms, a straight-chain alkoxy group having 1 to 3 carbon atoms, or a terminal having the number of carbon atoms A linear alkyl group having 1 to 5 carbon atoms substituted with 1 to 3 alkoxy
- Ring G, Ring H, Ring I and Ring J are each independently a trans-1,4-cyclohexylene group, a transdecahydronaphthalene-trans-2,6-diyl group, 1 to 2 fluorine atoms or 1,4-phenylene group optionally substituted by a methyl group, naphthalene-2,6-diyl group optionally substituted by one or more fluorine atoms, substituted by 1 or 2 fluorine atoms
- the other ring is a trans-1,4-cyclohexylene group or a 1,4-phenylene group optionally substituted by 1 to 2 fluorine atoms or a methyl group.
- the total number of fluorine atoms present in ring G, ring H, ring I and ring J is preferably 2 or less, and preferably 0 or 1.
- L g , L h and Li are each a linking group and each independently represents a single bond, an ethylene group (—CH 2 CH 2 —), a 1,2-propylene group (—CH (CH 3 ) CH 2 — and ) —CH 2 CH (CH 3 ) —), 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CH ⁇ CH—, —CH ⁇ CF—, —CF ⁇ CH—, —CF ⁇ CF—, —C ⁇ C— or —CH ⁇ NN ⁇ CH—, each represents a single bond, ethylene group, 1,4-butylene group, —COO—, —OCO—, —OCF 2 —, —CF 2 O—, —CF ⁇ CF—, —C ⁇ C— or —CH ⁇ NN ⁇ CH— are preferred, and in general formula (C2), at least one of them is represented by formula (C3 ), At least two of them preferably represent
- the compounds represented by the general formulas (C1) to (C3) exclude the compounds represented by the general formulas (A1) to (A3) and the compounds represented by the general formulas (B1) to (B3).
- the fifth component is an optically active compound used for inducing a helical structure in the liquid crystal composition.
- a compound having an asymmetric carbon atom is preferable, and a compound having a 1-methylheptyloxy group is more preferable.
- the sixth component is a compound having a polymerizable functional group that can be polymerized by ultraviolet irradiation or heating, which is added to improve the response speed or improve the orientation of the liquid crystal composition.
- the polymerizable group is preferably an acryloxy group or a methacryloxy group, and more preferably a methacryloxy group.
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 4 and X 2 are each independently R in General Formula (2) or General Formula (3)). 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 4, and X 2 ).
- ether solvents such as tetrahydrofuran and diethyl ether are preferred. These solvents may be used alone or in combination.
- the azodicarboxylic acids are preferably diisopropyl azodicarboxylate or diethyl azodicarboxylate, and more preferably diisopropyl azodicarboxylate.
- triphenylphosphine is preferable.
- the reaction temperature at this time is a temperature at which the reaction proceeds suitably. Any of these may be used, but a range of ⁇ 20 ° C. to 30 ° C. is preferable, and a range of ⁇ 10 ° C. to 20 ° C. is more preferable. After adding azodicarboxylic acid esters, it is preferable to carry out the reaction at room temperature.
- X 1 is preferably a bromine atom, an iodine atom, a tosyloxy group, a mesyloxy group or a trifluoromethanesulfonyloxy group, more preferably a bromine atom, an iodine atom or a trifluoromethanesulfonyloxy group.
- any solvent can be used as long as it allows the reaction to proceed suitably, but ether solvents such as tetrahydrofuran and diethyl ether, alkyl nitrile solvents such as acetonitrile, ketone solvents such as acetone and methyl ethyl ketone, benzene, toluene and the like.
- Aromatic solvents such as amide solvents such as dimethylformamide and dimethylacetamide are preferred, and tetrahydrofuran, acetonitrile, acetone, methyl ethyl ketone, dimethylformamide and dimethylacetamide are more preferred. These solvents may be used alone or in combination.
- the base may be any as long as it allows the reaction to proceed smoothly.
- Alkali metal hydrides such as sodium hydride and potassium hydride, alkali hydroxide salts such as sodium hydroxide and potassium hydroxide, water Preferred are alkaline earth metal hydroxides such as barium oxide and calcium hydroxide, carbonates such as potassium carbonate and cesium carbonate, and tertiary alkylamines such as triethylamine and ethyldiisopropylamine.
- n is 1 and A 2 is a tetrahydropyranyl group, dioxane group or cyclohexyl group, sodium hydride is particularly preferable.
- a base other than alkali metal hydrides may be used as an aqueous solution.
- reaction temperature in the production in (a) may be any temperature as long as the reaction proceeds smoothly, but a temperature from room temperature to reflux of the solvent is preferred.
- the reaction temperature in the production in (b) may be any temperature that allows the reaction to proceed smoothly, but is preferably a temperature from 0 ° C. to the reflux of the solvent, and in particular, an alkali metal hydride is used as the base.
- the compound represented by the general formula (3) is preferably added at 0 ° C. to 20 ° C., more preferably 0 ° C. to 10 ° C., represented by the general formula (3). After the compound to be added is added, any temperature from room temperature to reflux of the solvent is preferred. (Production Method 3) Production Method of Compound Represented by General Formula (5) Via Phenylgrunard Reagent Phenyl Grignard reagent obtained by reacting the compound represented by General Formula (4) with magnesium metal Reaction with acid esters, hydrolysis or further reaction with alcohols or glycols as required to give a general formula (5)
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n and Y 4 are each independently R 1 , A 1 , A 2 , A in General Formula (1). 3 , Z 1 , Z 2 , m, n and Y 4 represent the same meaning, and X 3 is
- R 2 and R 3 each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms
- E represents — (CH 2 ) p — in which one or more hydrogen atoms present in the group may each independently be substituted with a methyl group; p represents 2, 3 or 4. ).
- X 2 is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably a bromine atom.
- Any solvent can be used as long as it allows the reaction to proceed smoothly.
- Ether solvents such as tetrahydrofuran, diethyl ether, diisopropyl ether, tert-butyl methyl ether (tertiary butyl methyl ether), hexane, toluene, and the like
- hydrocarbon solvents such as tetrahydrofuran, diethyl ether, and tert-butyl methyl ether are more preferable. These solvents may be used alone or in combination.
- boric acid esters trimethyl borate and triisopropyl borate are preferable.
- alcohols or glycols used as necessary methanol, ethanol, isopropyl alcohol, ethylene glycol, neopentyl glycol or 1,1,2,2-tetramethylethylene glycol is preferable, ethylene glycol or neopentyl glycol Is more preferable.
- the reaction temperature for preparing the phenyl Grignard reagent may be any temperature that allows the reaction to proceed smoothly, but is preferably a temperature from 0 ° C. to the reflux of the solvent, and from 30 ° C. to the reflux of the solvent. The temperature is more preferable.
- the reaction temperature for reacting the obtained phenyl Grignard reagent with borate esters is preferably from ⁇ 20 ° C. to 20 ° C., more preferably from 0 ° C. to 10 ° C.
- X 2 is preferably a chlorine atom, a bromine atom or an iodine atom, and more preferably X 2 is a bromine atom or an iodine atom.
- Ether solvents such as tetrahydrofuran and diethyl ether, hydrocarbon solvents such as hexane and heptane are preferable, and tetrahydrofuran or diethyl ether is more preferable. These solvents may be used alone or in combination.
- an alkyl metal is preferable, an alkyl lithium is preferable, and alkyl lithiums such as n-butyl lithium (normal butyl lithium), sec-butyl lithium (secondary butyl lithium), and tert-butyl lithium (tertiary butyl lithium) are used.
- n-butyllithium is more preferable.
- Any boric acid ester may be used as long as the reaction proceeds smoothly, but trimethyl borate and triisopropyl borate are preferable, and triisopropyl borate is more preferable.
- alcohols or glycols used as necessary methanol, ethanol, isopropyl alcohol, ethylene glycol, neopentyl glycol or 1,1,2,2-tetramethylethylene glycol is preferable, ethylene glycol or neopentyl glycol Is more preferable.
- the temperature for preparing the phenyllithiums may be any temperature that allows the reaction to proceed smoothly, but is preferably in the range of ⁇ 78 ° C. to ⁇ 30 ° C., and is ⁇ 78 ° C. to ⁇ 60 ° C. Is more preferable.
- the temperature is preferably ⁇ 78 ° C. to ⁇ 40 ° C. After the boric acid ester is added, the temperature is slowly raised from 0 ° C. to 20 ° C. Is preferred.
- alkyllithiums such as n-butyllithium, s-butyllithium and tert-butyllithium, alkyllithium amides such as lithium diisopropylamide and lithium dibutylamide are preferred, and butyllithium or lithium diisopropylamide is more preferred.
- Any boric acid ester may be used as long as the reaction proceeds smoothly, but trimethyl borate and triisopropyl borate are preferable, and triisopropyl borate is more preferable.
- alcohols or glycols used as necessary methanol, ethanol, isopropyl alcohol, ethylene glycol, neopentyl glycol or 1,1,2,2-tetramethylethylene glycol is preferable, ethylene glycol or neopentyl glycol Is more preferable.
- solvents may be used alone or in combination.
- the temperature for preparing the phenyllithium derivative may be any temperature that allows the reaction to proceed smoothly, but is preferably in the range of ⁇ 78 ° C. to ⁇ 10 ° C., and is ⁇ 78 ° C. to ⁇ 40 ° C. Is more preferable.
- the temperature is preferably from ⁇ 78 ° C. to ⁇ 10 ° C. After boric acid esters are added, the temperature is slowly raised from 0 ° C. to 20 ° C. Is preferred.
- X 4 represents a trifluoromethanesulfonyloxy group, a chlorine atom, a bromine atom or an iodine atom
- Y 1 , Y 2 and Y 3 each independently represent a hydrogen atom, a fluorine atom or a chlorine atom
- R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 1 , Y 2 , Y 3 and Y 4 are each independently represented by General Formula (5) and General It represents the same meaning as R 1 , A 1 , A 2 , A 3 , Z 1 , Z 2 , m, n, Y 1 , Y 2 , Y 3 and Y 4 in Formula (6)). the compound obtained it is possible.
- any solvent can be used as long as it allows the reaction to proceed smoothly, but ether solvents such as tetrahydrofuran, diethyl ether and tert-butyl methyl ether, alcohol solvents such as ethanol, and ketone solvents such as acetone and methyl ethyl ketone.
- Solvents, amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide, and aromatic hydrocarbon solvents such as benzene and toluene are preferred, tetrahydrofuran, ethanol, acetone, methyl ethyl ketone, N, N-dimethylformamide, More preferred is toluene.
- solvents may be used alone or in combination.
- Any transition metal catalyst may be used as long as the reaction proceeds smoothly. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphino) palladium dichloride ( II), palladium-based transition metal catalysts such as [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or nickel-based transition metal catalysts such as tetrakistriphenylphosphine palladium (0), palladium acetate More preferred is (II) or [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride. Moreover, in order to accelerate
- the base may be any as long as it allows the reaction to proceed smoothly, but amine reagents such as triethylamine and ethyldiisopropylamine, carbonates such as potassium carbonate and cesium carbonate, or sodium hydroxide and potassium hydroxide. Alkali metal hydroxides are preferred, and carbonates such as potassium carbonate and cesium carbonate are more preferred. These bases may be used as an aqueous solution as necessary.
- reaction temperature is preferably from 0 ° C. to the range where the solvent is refluxed, and more preferably from 40 ° C. to 110 ° C.
- any solvent can be used as long as the reaction proceeds smoothly.
- Ether solvents such as tetrahydrofuran, diethyl ether, and tert-butyl methyl ether, and aromatic hydrocarbon solvents such as benzene, toluene, and xylene can be used. Tetrahydrofuran, tert-butyl methyl ether, toluene or xylene is more preferred. These solvents may be used alone or in combination.
- Any transition metal catalyst may be used as long as the reaction proceeds smoothly. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphino) palladium dichloride ( II), palladium-based transition metal catalysts such as [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or nickel-based transition metal catalysts such as tetrakistriphenylphosphine palladium (0), palladium acetate More preferred is (II) or [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride. Further, a phosphine-based ligand may be added to promote the progress of the reaction.
- the reaction temperature may be any temperature as long as the reaction proceeds smoothly, but is preferably a temperature from 0 ° C. to reflux of the solvent, more preferably from 60 ° C. to 110 ° C.
- X 2 is a chlorine atom
- an ether compound is a bromine atom or an iodine atom
- a phenyl lithiums such X 3 is Li in the general formula obtained by reacting with alkyl metals (5)
- the obtained compound is used as it is or after conversion of the metal species by a metal exchange reaction as necessary, and then reacted with the fluorinated naphthalene derivative represented by the general formula (6) in the presence of a transition metal catalyst.
- a compound represented by the general formula (1) can be obtained.
- Any solvent can be used as long as it allows the reaction to proceed smoothly.
- Ether solvents such as tetrahydrofuran, diethyl ether, and tert-butyl methyl ether, hydrocarbon solvents such as hexane and heptane, toluene, xylene, and the like
- Aromatic hydrocarbon solvents are preferred, and tetrahydrofuran or tert-butyl methyl ether is more preferred.
- These solvents may be used alone or in combination.
- Any transition metal catalyst may be used as long as the reaction proceeds smoothly. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphino) palladium dichloride ( II), palladium-based transition metal catalysts such as [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or nickel-based transition metal catalysts such as tetrakistriphenylphosphine palladium (0), palladium acetate More preferred is (II) or [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride. Further, a phosphine-based ligand may be added to promote the progress of the reaction.
- n-butyl lithium, sec-butyl lithium, tert-butyl lithium and the like are preferable, and n-butyl lithium is more preferable.
- Zinc chloride or magnesium chloride is preferred as the metal salt used in the metal exchange reaction performed as necessary.
- a compound in which X 3 is ZnCl in the general formula (5) can be produced by using zinc chloride, and a compound in which X 3 is MgCl in the general formula (5) can be prepared by using magnesium chloride. Can be manufactured.
- the reaction temperature may be any temperature that allows the reaction to proceed smoothly, but is preferably -76 ° to -40 ° C, more preferably -76 ° C to -60 ° C.
- phenyl lithium obtained by reacting a compound in which X 2 is a hydrogen atom and A 3 is the general formula (B-1) or (B-2) with a base is used as it is.
- the compound represented by the general formula (1) is obtained by reacting with the compound represented by the general formula (6) in the presence of a transition metal catalyst. I can do it.
- Any solvent can be used as long as it allows the reaction to proceed smoothly.
- Ether solvents such as tetrahydrofuran, diethyl ether, and tert-butyl methyl ether, hydrocarbon solvents such as hexane and heptane, toluene, xylene, and the like
- Aromatic hydrocarbon solvents are preferred, and tetrahydrofuran or tert-butyl methyl ether is more preferred.
- These solvents may be used alone or in combination.
- Any transition metal catalyst may be used as long as the reaction proceeds smoothly. Tetrakis (triphenylphosphine) palladium (0), palladium (II) acetate, bis (triphenylphosphino) palladium dichloride ( II), palladium-based transition metal catalysts such as [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) or nickel-based transition metal catalysts such as tetrakistriphenylphosphine palladium (0), palladium acetate More preferred is (II) or [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride. Further, a phosphine-based ligand may be added to promote the progress of the reaction.
- the base is preferably an alkyllithium reagent such as n-butyllithium, sec-butyllithium or tert-butyllithium, or lithium diisopropylamide, and more preferably n-butyllithium or lithium diisopropylamide.
- alkyllithium reagent such as n-butyllithium, sec-butyllithium or tert-butyllithium, or lithium diisopropylamide, and more preferably n-butyllithium or lithium diisopropylamide.
- zinc chloride or magnesium chloride is preferable.
- the reaction temperature may be any as long as it allows the reaction to proceed smoothly.
- alkyl lithiums when used as the base, ⁇ 76 ° to ⁇ 40 ° C. is preferable, and ⁇ 76 ° C. to ⁇ 60 ° C. is more preferable.
- the temperature is preferably from -76 ° C to -10 ° C, more preferably from -40 ° C to -20 ° C.
- the phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC).
- T n-i nematic phase - represents the transition temperature of the isotropic phase.
- THF Tetrahydrofuran
- DMF N, N-dimethylformamide
- DIAD Diisopropyl azodicarboxylate
- TPP Triphenylphosphine Me: Methyl group, Pr: n-propyl group, Bu: n-butyl group
- Tf Trifluoromethanesulfonyl group
- LDA Lithium diisopropyl Preparation of Amide (Example 1) [4- (5,6,7-trifluoronaphthalen-2-yl) phenyl]-(2,6-difluoro-4-propylphenyloxy) methane
- DIAD (61.7 g) was added at such a rate that the internal temperature did not become 5 ° C. or higher, and the mixture was stirred at room temperature for 3 hours.
- the precipitate was removed by filtration, a 65% aqueous methanol solution (600 mL) was added to the filtrate, and the mixture was separated, and the organic layer was separated.
- the organic layer was washed with 65% aqueous methanol (500 mL) and saturated brine (500 mL) in this order.
- Trans-4- (3,5-difluorophenyl) cyclohexanecarbaldehyde (112 g) is dissolved in ethanol (224 mL), THF (30 mL) and water (30 mL), and hydrogenated at an external temperature of 5 ° C.
- Sodium chloride (9.4 g) was slowly added and stirred at an external temperature of 5 ° C. for 10 minutes.
- the reaction solution was slowly poured into 10% hydrochloric acid (450 mL) and stirred for 30 minutes.
- [4- (3,5-difluorophenyl) phenyl]-(3,5-difluoro-4-propylphenyl) methane (40.6 g) was dissolved in THF (200 mL) at such a rate that the internal temperature did not become ⁇ 35 or higher. The solution was added, and the mixture was further stirred at ⁇ 40 ° C. for 1 hour. Zinc chloride (17.7 g) was slowly added at such a rate that the internal temperature did not exceed ⁇ 35 ° C., stirred at ⁇ 40 ° C. for another 30 minutes, and slowly warmed to room temperature to prepare an organozinc reagent. .
- Example 2 A (39.4 g) and tetrakistriphenylphosphine palladium (0) (2.5 g) obtained in (1-1) of Example 1 were dissolved in THF (200 mL) in a separate reaction vessel under a nitrogen atmosphere. The previously prepared organozinc reagent solution was added and stirred at room temperature for 10 hours. Under ice cooling, 10% hydrochloric acid (300 mL) was slowly added to the reaction solution, toluene (300 mL) was added, and the organic layer was separated. Toluene was added to the aqueous layer for liquid separation, the organic layers were combined, and the organic layer was washed 3 times with saturated brine.
- the mixture was dissolved in 250 mL) and stirred for 2 hours while removing water produced under reflux. After allowing to cool to room temperature, the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, dried by adding sodium sulfate, and the solvent was distilled off under reduced pressure. Subsequently, the entire amount obtained was dissolved in ethyl acetate (280 mL), 5% palladium / carbon (7.1 g) was added, and the mixture was stirred at 5 MPa in a hydrogen atmosphere for 6 hours. After filtering off the palladium catalyst, the solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography.
- Example 1 except that 5,6-difluoro-2-naphthol is used instead of 5,6,7-trifluoro-2-naphthol in (1-1) of Example 1.
- the reaction was carried out in the same manner as in 1 to obtain 5,6-difluoronaphthalen-2-yl trifluoromethanesulfonate (B, 34.3 g) as a colorless transparent liquid.
- (6-2) The same method as in Example 4-1, except that 2-fluoro-4-methylphenol is used instead of 2,6-difluoro-4-propylphenol in (4-1) of Example 4.
- a liquid crystal composition (MA) comprising 20% methane was prepared. The physical properties of this composition are as follows.
- Example 8 Preparation of Liquid Crystal Composition-2 [Trans-4- (4- (5,6,7-trifluoronaphthalen-2-yl) -3,5-difluorophenyl) cyclohexyl)-obtained in Comparative Example 3 with 95% of the base liquid crystal (H)
- a liquid crystal composition (MB) comprising 5% of (2,6-difluoro-4-propylphenyloxy) methane was prepared.
- the physical properties of this composition are as follows.
- T n-i 117.9 °C ⁇ : 5.93 ⁇ n: 0.0949 ⁇ 20 : 23.8 mPa ⁇ s
- the prepared liquid crystal composition (MB) maintained a uniform nematic liquid crystal state for more than one month at room temperature, and thus was found to exhibit high miscibility with the liquid crystal composition.
- Preparation of (Example 9) The liquid crystal composition -3 [4- (5,6,7-trifluoronaphthalen-2-yl) phenyl]-[2,6-difluoro-4- (trans-4) obtained in 80% of the base liquid crystal (H) and Comparative Example 5
- a liquid crystal composition (MC) consisting of 20% of (propylpropyl) phenyloxy] methane was prepared.
- the physical properties of this composition are as follows.
- T n ⁇ i 130.8 ° C.
- T n ⁇ i 120.6 ° C.
- MD prepared liquid crystal composition
- Example 7 By comparing Comparative Example 2 to Example 7, the present invention compounds although T n-i and ⁇ n decreases as compared with the comparative compound, [Delta] [epsilon] is sufficiently large, it is understood that further large effect of suppressing the viscosity increase . Since Example 7 and Comparative Example 1 differ in the amount added to the base liquid crystal, comparison was made using extrapolated values when the concentration was 100%. Moreover, it turned out that the liquid-crystal composition which uses the compound represented by General formula (1) as a structural component shows a stable nematic phase over a long period of time.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Nonlinear Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- General Physics & Mathematics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
Description
A1は
(a)1,4-シクロへキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は各々独立してO-又は-S-に置き換えられても良い。)
(b)1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良く、この基中に存在する水素原子はフッ素原子に置換されても良い。)
からなる群より選ばれる基であり、
Z1は-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-、-CF=CF-、-C≡C-又は単結合を表し、
Y4は水素原子、フッ素原子又は塩素原子を表し、
mは0又は1を表す。)で表される化合物と、一般式(3)
A3は1,4-フェニレン基(この基中に存在する水素原子はフッ素原子に置換されても良い。)を表し、
X1はヒドロキシ基、塩素原子、臭素原子、ヨウ素原子、トシルオキシ基、メシルオキシ基又はトリフルオロメタンスルホニルオキシ基を表し、
X2は塩素原子、臭素原子又はヨウ素原子表すが、A3が(A-1)又は(A-2)
Z2は一般式(2)におけるZ1と同様な意味を表し、
nは0又は1を表す。)で表される化合物を、X1がヒドロキシル基である場合は脱水縮合剤の存在下縮合させ、又はX1が塩素原子、臭素原子、ヨウ素原子、トシルオキシ基、メシルオキシ基又はトリフルオロメタンスルホニルオキシ基である場合は塩基の存在下エーテル化反応させる事により、一般式(4)
X3はMgX4、Li、ZnX4、CuX4(式中、X4は塩素原子、臭素原子又はヨウ素原子を表す。)を表すか一般式(B-1)又は(B-2)
Eは基中に存在する一つ以上の水素原子が各々独立してメチル基に置換されていても良い-(CH2)p-を表し、
pは2、3又は4を表す。)で表す置換基を表す。)
で表される化合物へ誘導した後、一般式(6)
X5はトリフルオロメタンスルホニルオキシ基、塩素原子、臭素原子又はヨウ素原子を表す。)で表される化合物と遷移金属触媒存在下反応させる一般式(1)
A1は
(a)1,4-シクロへキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は各々独立してO-又は-S-に置き換えられても良い。)
(b)1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良く、この基中に存在する水素原子はフッ素原子に置換されても良い。)
からなる群より選ばれる基であり、
Z1は-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-、-CF=CF-、-C≡C-又は単結合を表し、
Y4は水素原子、フッ素原子又は塩素原子を表し、
mは0又は1を表す。)で表される化合物と、一般式(3)
A3は1,4-フェニレン基(この基中に存在する水素原子はフッ素原子に置換されても良い。)を表し、
X1はヒドロキシ基、塩素原子、臭素原子、ヨウ素原子、トシルオキシ基、メシルオキシ基又はトリフルオロメタンスルホニルオキシ基を表し、
X2は塩素原子、臭素原子又はヨウ素原子表すが、A3が(A-1)又は(A-2)
Z2は一般式(2)におけるZ1と同様な意味を表し、
nは0又は1を表す。)で表される化合物を、X1がヒドロキシル基である場合は脱水縮合剤の存在下縮合させ、又はX1が塩素原子、臭素原子、ヨウ素原子、トシルオキシ基、メシルオキシ基又はトリフルオロメタンスルホニルオキシ基である場合は塩基の存在下エーテル化反応させる事により、一般式(4)
X3はMgX4、Li、Na、ZnX4又はCuX4(式中、X4は塩素原子、臭素原子又はヨウ素原子を表す。)を表すか一般式(B-1)又は(B-2)
Eは基中に存在する一つ以上の水素原子が各々独立してメチル基に置換されていても良い-(CH2)p-を表し、
pは2、3又は4を表す。)で表す置換基を表す。)
で表される化合物を製造する事が出来る。次工程の収率を考慮した場合、X3はX4が臭素原子又は塩素原子であるMgX4又はZnX4であるか、R2及びR3が水素原子である一般式(B-1)又はpが2又は3である一般式(B-2)である事が好ましい。
一般式(6)
X5はトリフルオロメタンスルホニルオキシ基、塩素原子、臭素原子又はヨウ素原子を表す。)で表される化合物と遷移金属触媒存在下反応させる一般式(1)
本発明の液晶組成物において一般式(1)で表される化合物の含有量が少ないとその効果が現れないため、液晶組成物中に下限値として、1%(組成物中の%は質量%を表す。)が好ましく、2%が好ましく、5%が更に好ましい。又、含有量が多いと析出等の問題を引き起こすため、上限値としては、50%が好ましく、30%がより好ましく、20%が更に好ましく、10%が特に好ましい。一般式(1)で表される化合物は1種のみで使用することもできるが、2種以上の化合物を同時に使用してもよい。
(製法1)脱水縮合剤を用いる一般式(4)で表される化合物の製造方法
一般式(2)
(製法2)塩基を用いるエーテル化による、一般式(4)で表される化合物の製造方法
一般式(2)で表される化合物を、一般式(3)で表される化合物と、塩基の存在下反応させる事で一般式(4)で表される化合物を得る事が出来る。
(a)使用する全ての原料及び溶媒を室温にて混合し必要に応じて加熱する。
(b)一般式(2)で表される化合物と塩基の溶液又は懸濁溶液を必要に応じて加熱しておき、そこに一般式(3)で表される化合物の溶液を加える。
のどちらで行っても良い。(a)で製造する場合の反応温度は、反応を円滑に進行させる温度であればいずれでも構わないが、室温から溶媒が環流するまでの温度が好ましい。(b)で製造する場合の反応温度は、反応を円滑に進行させる温度であればいずれでも構わないが、0℃から溶媒が環流するまでの温度が好ましく、特に塩基に水素化アルカリ金属類を用いる場合に於いて一般式(3)で表される化合物を加える際には0℃から20℃である事が好ましく、0℃から10℃である事が更に好ましく、一般式(3)で表される化合物を加えた後は室温から溶媒が環流するまでのいずれかの温度が好ましい。
(製法3)フェニルグルニャール試薬を経由する一般式(5)で表される化合物の製造方法
一般式(4)で表される化合物を、金属マグネシウムと反応させて得られるフェニルグリニャール試薬をホウ酸エステル類と反応させ、加水分解又はさらに必要に応じてアルコール又はグリコール類と反応させることにより、一般式(5)
Eは基中に存在する一つ以上の水素原子が各々独立してメチル基に置換されていても良い-(CH2)p-を表し、
pは2、3又は4を表す。)を表す。)で表される化合物を得る事が出来る。
(製法4)フェニルリチウム類を経由する一般式(5)で表される化合物の製造方法-1
一般式(4)で表される化合物を、有機金属類と反応させて得られるフェニルリチウム類をホウ酸エステル類と反応させ、加水分解又はさらに必要に応じてアルコール又はグリコール類と反応させることにより、一般式(5)で表される化合物を得る事が出来る。
(製法5)フェニルリチウム類を経由する一般式(5)で表される化合物の製造方法-2
一般式(4)において、X2が水素原子でありかつA3が一般式(B-1)又は(B-2)で表される基である化合物を、フェニルリチウム誘導体とした後、(製法4)と同様の製造方法により、一般式(5)で表される化合物を得る事が出来る。
(製法6)一般式(5)で表される化合物から一般式(1)で表される化合物の製造方法
一般式(5)において、X3が一般式(B-1)又は(B-2)であるフェニルホウ酸誘導体と一般式(6)
(a)使用する原料及び溶媒を全て混合しておき加熱する。
(b)一般式(5)で表されるフェニルホウ酸誘導体以外の原料及び溶媒を混合しておき、必要に応じて加熱しながら、一般式(5)で表されるフェニルホウ酸誘導体の溶液を加える。
のどちらの方法で行っても良く、(a)及び(b)共に反応温度は0℃から溶媒が還流する範囲までの温度が好ましく、40℃から110℃までが更に好ましい。
(製法7)一般式(4)で表される化合物から一般式(1)で表される化合物の製造方法-1
一般式(4)において、X2が塩素原子、臭素原子、ヨウ素原子であるエーテル化合物を、金属マグネシウムと反応させて得られる一般式(5)においてX3がMgX4であるフェニルグリニャール試薬とした後、一般式(6)で表される化合物と遷移金属触媒存在下反応させ、一般式(1)で表される化合物を得る事が出来る。
(製法8)一般式(4)で表される化合物から一般式(1)で表される化合物の製造方法-2
一般式(4)において、X2は塩素原子、臭素原子又はヨウ素原子であるエーテル化合物を、アルキル金属類と反応させて得られる一般式(5)においてX3がLiであるフェニルリチウム類を製造した後、得られた化合物をそのまま用いるか又は必要に応じて金属交換反応により金属種を変換した後に、一般式(6)で表されるフッ素化ナフタレン誘導体と遷移金属触媒存在下反応させる事で、一般式(1)で表される化合物を得る事が出来る。
(製法9)一般式(4)で表される化合物から一般式(1)で表される化合物の製造方法-3
一般式(4)において、X2は水素原子でありかつA3が一般式(B-1)又は(B-2)である化合物を、塩基と反応させて得られるフェニルリチウム類を、そのまま用いるか又は必要に応じて金属交換反応により金属種を変換した後に一般式(6)で表される化合物と遷移金属触媒存在下反応させる事で、一般式(1)で表される化合物を得る事が出来る。
DMF:N,N-ジメチルホルムアミド
DIAD:アゾジカルボン酸ジイソプロピル
TPP:トリフェニルホスフィン
Me:メチル基、Pr:n-プロピル基、Bu:n-ブチル基
Tf:トリフルオロメタンスルホニル基
LDA:リチウムジイソプロピルアミド
(実施例1)[4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタンの製造
(1-2) 窒素雰囲気下、3,5-ジフルオロプロピルベンゼン(134g,Molecular Crystals and Liquid Crystals、1995、260、93-106と同様な方法で合成した。)をTHF(650mL)に溶解させ、-40℃以下に冷却した。内温が-35℃以上の温度にならない速度で、1.6mol/Lのn-ブチルリチウム/ヘキサン溶液(640mL)を加え、-40℃にてさらに1時間撹拌した。続いて、-40℃にてトリメチルホウ酸(116g)をTHF(350mL)に溶解させた溶液を、内温が-35℃以上にならない速度で加えた。ゆっくりと室温まで昇温し、室温にて更に30分撹拌した後、氷冷下10%塩酸(400mL)を加えて有機層を分取し、飽和食塩水にて洗浄した。続いて、15%過酸化水素水(215g)をゆっくりと加えた後、40℃に加熱下6時間撹拌した。氷冷した後、20%亜硫酸ナトリウム水溶液(300mL)を内温が20℃を超えない速度で加え、有機層を分取した。水層に酢酸エチル(500mL)を加えて抽出し、有機層を併せて飽和食塩水にて洗浄し、硫酸ナトリウムを加えて乾燥した。溶媒を減圧留去した後、ヘキサン(800mL)を加えて不溶物を濾過により除去し、ろ過液を減圧濃縮する事で、黄色液体として2,6-ジフルオロ-4-プロピルフェノール(123g)を得た。
MS m/z:172[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=6.86(2H,d,J=8.4Hz),2.49(2H,t,J=7.2Hz),1.59(2H, quinted,j=7.4Hz),0.92(3H,t,J=7.3Hz)
(1-3) 2,6-ジフルオロ-4-プロピルフェノール(50g)、4-ブロモベンジルアルコール(54.2g)、トリフェニルホスフィン(83.7g)をTHF(300mL)に溶解させ、-10℃に冷却した。内温が5℃以上とならない速度でDIAD(61.7g)を加えた後、室温にて3時間撹拌した。水(5mL)を加えた後、溶媒を減圧留去した後、ヘキサン(600mL)と70%tert-ブチルヒドロぺルオキシド(10g)を加え、室温にて2時間撹拌した。析出物を濾過により除去し、ろ過液に65%メタノール水溶液(600mL)を加えて分液し、有機層を分取した。有機層を65%メタノール水溶液(500mL)、飽和食塩水(500mL)の順に洗浄した。硫酸ナトリウムを加えて乾燥し、溶媒を留去し、シリカゲルカラムクロマトグラフィーにより精製する事で、黄色液体として4-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]ブロモベンゼン(83.6g)を得た。
MS m/z:340,342[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=7.47(2H,d,J=8.2Hz),7.31(2H,d,J=8.4Hz),6.68(4H,d,j=9.0Hz),5.05(2H,s),2.48(2H,t,J=7.3Hz),1.59(2H,quinted,j=7.5Hz),0.91(3H,t,J=7.2Hz)
(1-4) 窒素雰囲気下、マグネシウム6.3gとTHF20mLの懸濁溶液に(2,6-ジフルオロ-4-プロピルフェニルオキシ)(4-ブロモフェニル)メタン(83.6g)をTHF(120mL)に溶解させた溶液を穏やかに還流する速度で滴下した。滴下後65℃にて3時間撹拌し、氷冷した。内温が10℃以上とならない速度でトリメチルホウ酸(28.0g)をTHF(100mL)に溶解させた溶液を加え、室温にて2時間撹拌した。10%塩酸を系内が酸性となるまで加え、室温にて30分撹拌した。有機層を分取し、水層にトルエンを加えて抽出し、有機層を併せ、飽和食塩水にて有機層を洗浄した。硫酸ナトリウムを加えて乾燥し、溶媒を減圧留去する事により、黄色液体として4-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]フェニルホウ酸(64.0g)を得た。
1HNMR(CDCl3、TMS内部標準)δ(ppm)=7.58(2H,d,J=7.7Hz),7.48(2H,d,J=8.3Hz),6.70(2H,d,j=7.4Hz),5.11(2H,s), 2.49(2H,t,J=7.3Hz),1.59(2H,quinted,j=7.5Hz),0.92(3H,t,J=7.2Hz)
(1-5) 窒素雰囲気下、4-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]フェニルホウ酸4-プロピルブロモベンゼン(8.0g)、(1-1)で得られたA(7.8g)、テトラキストリフェニルホスフィンパラジウム(0)(0.55g)、2M炭酸カリウム水溶液(18mL)及びTHF40mLを混合させた溶液を60℃にて4時間撹拌した。放冷後、水、トルエンを加え分液し、有機層を飽和食塩水にて洗浄し、硫酸ナトリウムを加えて乾燥し、溶媒を減圧留去した。シリカゲルカラムクロマトグラフィーにより精製した後、エタノールから再結晶する事で、白色固体として[4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタン(2.8g)を得た。
MS m/z:442[M+]
相転移温度(℃):Cr 57.8 N 67.3 Iso
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.05(1H,d,J=8.7Hz),7.88(1H,s),7.75(1H,d,j=8.7Hz),7.65(2H,d,j=8.0Hz),7.56(2H,d,j=8.0Hz),7.40-7.35(1H,m),6.70(2H,d,j=8.5Hz),5.17(2H,s),2.49(2H,t,7.7Hz),1.59(2H,quintet,j=7.4Hz),0.92(3H,t,j=7.4Hz)
(実施例2)[3,5-ジフルオロ-4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタンの製造
MS m/z:298[M+]
1HNMR(CDCl3、TMS内部標準)δ(ppm)=6.99(2H,d,J=6.2Hz),6.78-6.68(3H,m),5.08(2H,s),2.50(2H,t,J=7.2Hz),1.60(2H, quinted,j=7.4Hz),0.92(3H,t,J=7.3Hz)
(2-2) 1,3-ジフルオロ-5-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]ベンゼン(10.0g)をTHF(50mL)に溶解させ、-70℃に冷却した。内温が-60℃以上とならない速度で1.6mol/Lのn-ブチルリチウム/ヘキサン溶液(23mL)を加え、-70℃にて30分間撹拌した。続いて、内温が-60℃を超えない速度で、トリメチルホウ酸(4.2g)をTHF(20mL)に溶解させた溶液を加えた後、ゆっくりと室温まで昇温させ、室温にて30分間撹拌した。氷冷し、10%塩酸、トルエンを加えて有機層を分取し、水層にトルエンを加えて抽出した。有機層を併せ、飽和食塩水にて洗浄し、硫酸ナトリウムを加えて乾燥した。溶媒を減圧留去する事で明黄色固体として、2,6-ジフルオロ-4-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]フェニルホウ酸(11.4g)を得た。
1HNMR(CDCl3、TMS内部標準)δ(ppm)=6.95(2H,d,J=6.8Hz),6.71(2H,d,j=8.7Hz),5.07(2H,s),2.50(2H,t,J=7.4Hz),1.61(2H, quinted,j=7.4Hz),0.93(3H,t,J=7.4Hz)
(2-3) 窒素雰囲気下、2,6-ジフルオロ-4-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]フェニルホウ酸(10.0g)、実施例1の(1-1)で得られたA(8.0g)、無水炭酸カリウム(5.0g)、テトラキストリフェニルホスフィンパラジウム(0)(0.56g)をアセトン(40mL)に溶解させ、加熱還流下6時間撹拌した。放冷後、水、トルエンを加えて有機層を分取し、水層にトルエンを加えて抽出し、有機層を併せ、飽和食塩水にて洗浄し、硫酸ナトリウムを加えて乾燥した。溶媒を減圧留去し、シリカゲルカラムクロマトグラフィーにより精製し、エタノールとアセトンの混合溶媒から再結晶する事で、白色固体として[3,5-ジフルオロ-4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタン(2.3g)を得た。
相転移温度(℃):Cr 128 Iso
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.11(1H,d,J=8.7Hz),7.87(1H,s),7.62(1H,d,j=8.64Hz),7.45-7.40(1H,m),7.14(2H,d,j=7.9Hz),6.74(2H,d,j=9.0Hz),5.14(1H,s),2.52(2H,t,j=7.3Hz),1.61(2H,quinted,j=7.5Hz),0.93(3H,t,j=7.3Hz)
(実施例3)[trans-4-(4-(5,6,7-トリフルオロナフタレン-2-イル)-3,5-ジフルオロフェニル)シクロヘキシル)-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタンの製造
(3-2) trans-4-(3,5-ジフルオロフェニル)シクロヘキサンカルバルデヒド(112g)をエタノール(224mL)、THF(30mL)及び水(30mL)に溶解し、外温5℃で水素化ほう素ナトリウム(9.4g)をゆっくり加え、外温5℃で10分撹拌した。反応溶液を10%塩酸(450mL)にゆっくりあけて30分間撹拌した後、有機層を分取し、水層を酢酸エチルで抽出し、有機層を合わせて飽和食塩水で2回洗浄した。無水硫酸ナトリウムで乾燥した後溶媒を減圧留去し、淡黄色液体として[trans-4-(3,5-ジフルオロフェニル)シクロヘキシル]メタノール(110g)を得た。
(3-3) 窒素雰囲気下、実施例1の(1-2)で得られた2,6-ジフルオロ-4-プロピルフェノール(70g)、[trans-4-(3,5-ジフルオロフェニル)シクロヘキシル]メタノール(83g)、トリフェニルホスフィン(110g)をTHF(400mL)に溶解し、DIAD(81.2g)を内温23℃以下で滴下した。室温で2時間攪拌後水(10mL)を加え、溶媒を減圧留去した。残渣にヘキサン(200mL)、水(20mL)、メタノール(300mL)を加え、有機層を分取し、水層をヘキサンで抽出した後有機層を合わせ、50%メタノール水溶液2回、飽和食塩水の順で洗浄した。得られた溶液をシリカゲルカラムクロマトグラフィーで精製した後、エタノールから再結晶する事で、無色固体として[trans-4-(3,5-ジフルオロフェニル)シクロヘキシル)-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタン(80g)を得た。
(3-4) 窒素雰囲気下、[trans-4-(3,5-ジフルオロフェニル)シクロヘキシル)-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタン(40g)をTHF(400mL)に溶解し-60℃に冷却し、内温が-40℃以上にならない速度で1.6mol/Lのn-ブチルリチウム/ヘキサン溶液(70mL)を加え、-60℃にてさらに1時間撹拌した。続いて、ホウ酸トリメチル(13g)をTHF(50mL)に溶解させた溶液を内温が-40℃以上にならない速度で滴下した。内温0℃まで昇温後、10%塩酸を加えて酸性とした後、有機層を分取した。水層に酢酸エチルを加えて抽出し、有機層を合わせて飽和食塩水で2回洗浄後、無水硫酸ナトリウムで乾燥した。溶媒を減圧留去して、淡黄色固体として2,6-ジフルオロ-4-[trans-4-(2,6-ジフルオロ-4-プロピルフェニルオキシメチル)シクロヘキシル]フェニルホウ酸(44g)を得た。
(3-5) 窒素雰囲気下、2,6-ジフルオロ-4-[trans-4-(2,6-ジフルオロ-4-プロピルフェニルオキシメチル)シクロヘキシル]フェニルホウ酸(15g)、実施例1の(1-1)で得られたA(11.6g)、無水炭酸カリウム(7.3g)、テトラキストリフェニルホスフィンパラジウム(0)(0.82g)をアセトン(60mL)に溶解させ、加熱還流下8時間撹拌した。放冷後、水、トルエンを加えて有機層を分取し、水層にトルエンを加えて抽出し、有機層を併せ、飽和食塩水にて洗浄し、硫酸ナトリウムを加えて乾燥した。溶媒を減圧留去し、シリカゲルカラムクロマトグラフィーにより精製し、エタノールとアセトンの混合溶媒から再結晶する事で、白色固体としてtrans-4-(4-(5,6,7-トリフルオロナフタレン-2-イル)-3,5-ジフルオロフェニル)シクロヘキシル)-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタン(13.3g)を得た。
相転移温度(℃):Cr 125 N 192 Iso
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.10(1H,d,J=8.80Hz),7.87(1H,s),7.63(1H,d,=8.72Hz),7.43-7.39(1H,m),6.90(2H,d,J=8.88Hz),6.71(2H,d,J=8.96Hz),3.95(2H,d,J=6.28Hz),2.61-2.49(3H,m),2.12-2.01(4H,m),1.91-1.81(1H,m),1.65-1.46(4H,m),1.33-1.22(2H,m),0.93(3H,t,J=7.44Hz)
(実施例4) [4-(3,5-ジフルオロ-4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル)フェニル]-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタンの製造
(4-2) 窒素雰囲気下、4-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]ブロモベンゼン(48.1g)、酢酸パラジウム(II)(1.6g)、トリフェニルホスフィン(3.7g)をエタノール(480mL)に溶解させ、60℃に加熱した。3,5-ジフルオロフェニルホウ酸(26.7g)をエタノール(80mL)に溶解させた溶液をゆっくりと加え、60℃にてさらに5時間撹拌した。室温まで放冷後、反応液に水(1L)及びトルエン(400mL)を加え、有機層を分取した。有機層を飽和食塩水にて3回洗浄し、硫酸ナトリウムを加えて乾燥した。溶媒を減圧留去後、シリカゲルカラムクロマトグラフィーにて精製し、エタノール・アセトンの混合溶媒から再結晶する事で、白色固体として[4-(3,5-ジフルオロフェニル)フェニル]-(3,5-ジフルオロ-4-プロピルフェニル)メタン(40.6g)を得た。
(4-3) 窒素雰囲気下、ジイソプロピルアミン(14.3g)をTHF(140mL)に溶解し、-40℃に冷却した。内温が-35℃以上とならない速度で、1.6mol/Lのn-ブチルリチウム/ヘキサン溶液(75mL)を加え、-40℃にてさらに30分間撹拌した。内温が-35以上とならない速度で[4-(3,5-ジフルオロフェニル)フェニル]-(3,5-ジフルオロ-4-プロピルフェニル)メタン(40.6g)をTHF(200mL)に溶解させた溶液を加え、-40℃にてさらに1時間撹拌した。内温が-35℃以上とならない速度で塩化亜鉛(17.7g)をゆっくりと加え、-40℃にてさらに30分間撹拌し、ゆっくりと室温まで昇温する事で、有機亜鉛試薬を調製した。別の反応容器に窒素雰囲気下、実施例1の(1-1)で得られたA(39.4g)及びテトラキストリフェニルホスフィンパラジウム(0)(2.5g)をTHF(200mL)に溶解し、先に調製した有機亜鉛試薬溶液を加え、室温にて10時間撹拌した。氷冷下、反応液に10%塩酸(300mL)をゆっくりと加え、トルエン(300mL)を加え、有機層を分取した。水層にトルエンを加えて分液し、有機層を併せ、有機層を飽和食塩水にて3回洗浄した。硫酸ナトリウムを加えて乾燥し、シリカゲルカラムクロマトグラフィーにより精製し、さらにエタノール及びヘキサンから再結晶する事で、白色固体として[4-(3,5-ジフルオロ-4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル)フェニル]-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタン(34.2g)を得た。
(実施例5) [4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-[2,6-ジフルオロ-4-(trans-4-プロピルシクロヘキシル)フェニルオキシ]メタンの製造
(5-2) 窒素雰囲気下、粗製1-(1-ヒドロキシ-4-プロピルシクロヘキシル)-3,5-ジフルオロベンゼン(132g)及びp-トルエンスルホン酸1水和物(2.99g)をトルエン(250mL)に溶解させ、還流下生成する水を除去しながら2時間撹拌した。室温まで放冷後、飽和炭酸水素ナトリウム水溶液、飽和食塩水にて有機層を洗浄し、硫酸ナトリウムを加えて乾燥し、溶媒を減圧留去した。続いて、得られた全量を酢酸エチル(280mL)に溶解し、5%パラジウム/炭素(7.1g)を加え、水素雰囲気下5MPaにて6時間撹拌した。パラジウム触媒をろ過別した後、溶媒を減圧留去し、シリカゲルカラムクロマトグラフィーにて精製した。続いて、得られた全量及びtert-ブトキシカリウム(3.4g)をDMF(350mL)に溶解させ、室温にて4時間撹拌した。水とヘキサンを加え分液し、有機層を分取した。水層にヘキサンを加えて抽出し、有機層を併せ、飽和食塩水にて洗浄した。硫酸ナトリウムを加えて乾燥し、溶媒を留去し、減圧蒸留(206Pa、b.p.=110~112℃)する事により、無色透明液体として1-(トランス-4-プロピルシクロヘキシル)-3,5-ジフルオロベンゼン(58.1g)を得た。
(5-3) 窒素雰囲気下、1-(トランス-4-プロピルシクロヘキシル)-3,5-ジフルオロベンゼン(58.1g)をTHF(300mL)に溶解させ-40℃に冷却し、内温が-35℃を超えない速度で1.6mol/Lのn-ブチルリチウム/ヘキサン溶液(170mL)を加えた。-40℃にてさらに1時間撹拌した後、内温が-35以上とならない速度でホウ酸トリメチル(30.4g)をTHF(100mL)に溶解させた溶液を加え、-40℃にてさらに1時間撹拌した後、内温を室温まで昇温させた。氷冷した後、10%塩酸を系内が酸性となるまで加え、有機層を分取した。有機層を氷冷し、15%過酸化水素水溶液(60.8g)を加えた後、40℃に加熱して更に15時間撹拌した。10%亜硫酸ナトリウム水溶液を用いて過剰の過酸化水素を失活させた後、有機層を飽和食塩水に洗浄し、硫酸ナトリウムを加えて乾燥し、溶媒を減圧留去した。シリカゲルカラムクロマトグラフィーにより精製し、さらにヘキサンから再結晶する事により2,6-ジフルオロ-4-(trans-4-プロピルシクロヘキシル)フェノール(52.5g)を得た。
(5-4) 以下の工程は、実施例1における4-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]ブロモベンゼンに変えて2,6-ジフルオロ-4-(trans-4-プロピルシクロヘキシル)フェノールを用いる事以外は実施例1と同様な方法により反応を行う事で、白色固体として[4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-[2,6-ジフルオロ-4-(trans-4-プロピルシクロヘキシル)フェニルオキシ]メタン(54.4g)を得た。
相転移温度(℃):Cr 71 N 197 Iso
1HNMR(CDCl3、TMS内部標準)δ(ppm)=8.11(1H,d,J=8.80Hz),7.95(1H,s),7.80(1H,d,J=8.80Hz),7.69(2H,d,J=8.04Hz),7.59(2H,d,J=8.04Hz),7.46-7.41(1H,m),6.75(2H,d,J=9.6Hz),5.18(2H,s),2.42-2.36(1H,m),1.86(4H,d,J=11Hz),1.40-1.17(7H,m),1.06-0.97(2H,m),0.90(3H,t,J=7.28Hz)
(実施例6) [4-(5,6-ジフルオロナフタレン-2-イル)フェニル]-(2-フルオロ-4-メチルフェニルオキシ)メタン
(6-2) 実施例4の(4-1)における、2,6-ジフルオロ-4-プロピルフェノールの代わりに2-フルオロ-4-メチルフェノールを用いる以外は実施例4-1と同様な方法にてエーテル化を実施し、微黄色液体として4-[(2-フルオロ-4-メチルフェニルオキシ)メチル]ブロモベンゼン(23.5g)を得た。
(6-3) 実施例1の(1-4)における、4-[(2-フルオロ-4-メチルフェニルオキシ)メチル]ブロモベンゼンの代わりに4-[(2-フルオロ-4-プロピルフェニルオキシ)メチル]ブロモベンゼンを用いる以外は実施例1-4と同様な方法にて反応を実施し、黄色液体として粗製4-[(2-フルオロ-4-メチルフェニルオキシ)メチル]フェニルボロン酸(17.7g)を得た。
(6-4) 実施例1の(1-5)における、4-[(2,6-ジフルオロ-4-プロピルフェニルオキシ)メチル]フェニルホウ酸の代わりに4-[(2-フルオロ-4-メチルフェニルオキシ)メチル]フェニルボロン酸を用い、実施例1で製造方法を示したAの代わりにBを用いる以外は、実施例1の(1-5)と同様な方法にて反応を実施し、白色固体として[4-(5,6-ジフルオロナフタレン-2-イル)フェニル]-(2-フルオロ-4-メチルフェニルオキシ)メタン(11.7g)を得た。
(比較例1) 4-[4-(5,6,7-トリフルオロ-ナフタレン-2-イル)3-フルオロフェニル]プロピルベンゼンの製造
(実施例7) 液晶組成物の調製-1
以下の組成からなるホスト液晶組成物(H)
誘電率異方性(Δε):4.38
屈折率異方性(Δn):0.0899
粘度(η20):20.3mPa・s
この母体液晶(H)80%と、実施例1で得られた[4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタン20%からなる液晶組成物(M-A)を調製した。この組成物の物性値は以下の通りである。
Δε:9.20
Δn:0.1132
η20:25.9mPa・s
[4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタンの添加による効果として、Tn-iの低下が比較的小さく(外挿Tn-i=65.6℃)、Δεが正に大きくなり(外挿Δε=28.5)、Δnが大きく上昇し(外挿Δn=0.206)更に粘度上昇を比較的小さく抑える事が出来る(外挿η20=48.3mPa・s)ことが分かった。また、調製した液晶組成物(M-A)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、液晶組成物への高い混和性を示す事がわかった。
(実施例8) 液晶組成物の調製-2
母体液晶(H)95%と比較例3にて得られた[trans-4-(4-(5,6,7-トリフルオロナフタレン-2-イル)-3,5-ジフルオロフェニル)シクロヘキシル)-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタン5%からなる液晶組成物(M-B)を調製した。この組成物の物性値は以下の通りである。
Δε:5.93
Δn:0.0949
η20:23.8mPa・s
[trans-4-(4-(5,6,7-トリフルオロナフタレン-2-イル)-3,5-ジフルオロフェニル)シクロヘキシル)-(2,6-ジフルオロ-4-プロピルフェニルオキシ)メタンの添加の効果として、Tn-iを上昇させる事ができ(外挿Tn-i=137.9℃)、Δεを正に大きくし(外挿Δε=33.9)、Δnを大きく上昇させ(外挿Δn=0.237)、粘度上昇を比較的抑える事が出来る(外挿η20=101.1mPa・s)事がわかる。また、調製した液晶組成物(M-B)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、液晶組成物への高い混和性を示す事がわかった。
(実施例9) 液晶組成物の調製-3
母体液晶(H)80%と比較例5にて得られた[4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-[2,6-ジフルオロ-4-(trans-4-プロピルシクロヘキシル)フェニルオキシ]メタン20%からなる液晶組成物(M-C)を調製した。この組成物の物性値は以下の通りである。
Δε:8.10
Δn:0.1131
η20:30.5mPa・s
[4-(5,6,7-トリフルオロナフタレン-2-イル)フェニル]-[2,6-ジフルオロ-4-(trans-4-プロピルシクロヘキシル)フェニルオキシ]メタンの添加の効果として、Tn-iを大きく上昇させる事ができ(外挿Tn-i=186.6℃)、Δεを正に大きくし(外挿Δε=22.7)、Δnを大きく上昇させ(外挿Δn=0.216)、粘度上昇を比較的抑える事が出来る(外挿η20=73.7mPa・s)事がわかる。また、調製した液晶組成物(M-C)は、室温にて一ヶ月間以上均一なネマチック液晶状態を維持したことから、液晶組成物への高い混和性を示す事がわかった。
(比較例2) 液晶組成物の調製-2
母体液晶(H)85%と比較例1にて得られた4-[4-(5,6,7-トリフルオロ-ナフタレン-2-イル)3-フルオロフェニル]プロピルベンゼン15%からなる液晶組成物(M-D)を調製した。この組成物の物性値は以下の通りである。
Δε:7.10
Δn:0.1208
η20:26.0mPa・s
4-[4-(5,6,7-トリフルオロ-ナフタレン-2-イル)3-フルオロフェニル]プロピルベンゼンの添加の効果として、Tn-iを上昇させる事ができ(外挿Tn-i=139.9℃)、Δεを正に大きくし(外挿Δε=22.5)、Δnを極めて大きく上昇させ(外挿Δn=0.296)、粘度上昇を比較的抑える事が出来る(外挿η20=58.2mPa・s)事がわかる。しかしながら、調製した液晶組成物(M-D)は、室温にて三日後に結晶が析出したことから、ホスト液晶への混和性が比較的低い事が確認できた。
Claims (19)
- 一般式(2)
A1は
(a)1,4-シクロへキシレン基(この基中に存在する1個の-CH2-又は隣接していない2個以上の-CH2-は各々独立してO-又は-S-に置き換えられても良い。)
(b)1,4-フェニレン基(この基中に存在する1個の-CH=又は隣接していない2個以上の-CH=は-N=に置き換えられても良く、この基中に存在する水素原子はフッ素原子に置換されても良い。)
からなる群より選ばれる基であり、
Z1は-CH2O-、-OCH2-、-CF2O-、-OCF2-、-CH2CH2-、-CF2CF2-、-CH=CH-、-CF=CF-、-C≡C-又は単結合を表し、
Y4は水素原子、フッ素原子又は塩素原子を表し、
mは0又は1を表す。)で表される化合物と、一般式(3)
A3は1,4-フェニレン基(この基中に存在する水素原子はフッ素原子に置換されても良い。)を表し、
X1はヒドロキシ基、塩素原子、臭素原子、ヨウ素原子、トシルオキシ基、メシルオキシ基又はトリフルオロメタンスルホニルオキシ基を表し、
X2は塩素原子、臭素原子又はヨウ素原子表すが、A3が(A-1)又は(A-2)
Z2は一般式(2)におけるZ1と同様な意味を表し、
nは0又は1を表す。)で表される化合物を、X1がヒドロキシル基である場合は脱水縮合剤の存在下縮合させ、又はX1が塩素原子、臭素原子、ヨウ素原子、トシルオキシ基、メシルオキシ基又はトリフルオロメタンスルホニルオキシ基である場合は塩基の存在下エーテル化反応させる事により、一般式(4)
X3はMgX4、Li、Na、ZnX4又はCuX4(式中、X4は塩素原子、臭素原子又はヨウ素原子を表す。)を表すか一般式(B-1)又は(B-2)
Eは基中に存在する一つ以上の水素原子が各々独立してメチル基に置換されていても良い-(CH2)p-を表し、
pは2、3又は4を表す。)で表す置換基を表す。)
で表される化合物へ誘導した後、一般式(6)
X5はトリフルオロメタンスルホニルオキシ基、塩素原子、臭素原子又はヨウ素原子を表す。)で表される化合物と遷移金属触媒存在下反応させる一般式(1)
- 請求項1に記載の一般式(4)で表される化合物をアルカリ金属類、アルカリ土類金属類又は有機リチウム類と反応させることによる請求項1に記載の一般式(5)で表される化合物の製造方法。
- 請求項1に記載の一般式(2)で表される化合物と請求項1に記載の一般式(3)で表される化合物を脱水縮合剤としてアゾジカルボン酸類を用い、更にホスフィン類を用いて縮合させる請求項1記載の一般式(4)で表される化合物の製造方法。
- 請求項1に記載の一般式(2)で表される化合物と請求項1に記載の一般式(3)で表される化合物を塩基として水酸化アルカリ金属塩類、水酸化アルカリ土類金属塩類又は炭酸アルカリ金属塩類を用いてエーテル化させる請求項1記載の一般式(4)で表される化合物の製造方法。
- X2が塩素原子、臭素原子又はヨウ素原子である請求項1に記載の一般式(4)で表される化合物を、金属リチウム、金属ナトリウム、金属マグネシウム、n-ブチルリチウム、sec-ブチルリチウム又はtert-ブチルリチウムと反応させて、X3がMgX4、Li又はNa(式中、X4は塩素原子、臭素原子又はヨウ素原子を表す。)である請求項1記載の一般式(5)で表される化合物とした後、更にホウ酸エステル類と反応させる事で得られるX3が一般式(B-1)又は(B-2)で表される官能基である請求項1に記載の一般式(5)で表される化合物の製造方法。
- X2が水素原子である請求項1に記載の一般式(4)で表される化合物をn-ブチルリチウム、sec-ブチルリチウム、tert-ブチルリチウム又はジイソプロピルリチウムアミドと反応させて、X3がLiである請求項1記載の一般式(5)で表される化合物とした後、更にホウ酸エステル類と反応させる事で得られるX3が一般式(B-1)又は(B-2)で表される官能基である請求項1に記載の一般式(5)で表される化合物の製造方法。
- 一般式(5)で表される化合物と一般式(6)で表される化合物を遷移金属触媒としてパラジウム系遷移金属触媒又はニッケル系遷移金属触媒を用い、更に塩基を添加する請求項1に記載の一般式(1)で表される化合物の製造方法。
- 一般式(1)において、Y4がフッ素原子を表す請求項10又は11に記載の化合物。
- 一般式(1)において、Y3が水素原子を表す請求項10から12のいずれか一項に記載の化合物。
- 一般式(1)において、Y1及びY2がフッ素原子を表す請求項10から13のいずれか一項に記載の化合物。
- 一般式(1)において、mが0を表す請求項10から14のいずれか一項に記載の化合物。
- 一般式(1)において、nが1を表す請求項10から15のいずれか一項に記載の化合物。
- 一般式(1)において、nが0を表す請求項12から15のいずれか一項に記載の化合物。
- 請求項10から17のいずれか一項に記載の化合物を一種又は二種以上含有する液晶組成物。
- 請求項18記載の液晶組成物を使用した液晶表示素子。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201280036957.0A CN103717563B (zh) | 2011-12-26 | 2012-12-20 | 具有2-氟苯基氧基甲烷结构的化合物 |
KR20137031494A KR101488313B1 (ko) | 2011-12-26 | 2012-12-20 | 2-플루오로페닐옥시메탄 구조를 가지는 화합물 |
JP2013526263A JP5382268B1 (ja) | 2011-12-26 | 2012-12-20 | 2−フルオロフェニルオキシメタン構造を持つ化合物 |
US14/346,498 US9079836B2 (en) | 2011-12-26 | 2012-12-20 | Compound having 2-fluorophenyloxymethane structure, a method for preparing the same, a liquid crystal composition and a liquid crystal device |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011-283306 | 2011-12-26 | ||
JP2011283306 | 2011-12-26 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2013099754A1 true WO2013099754A1 (ja) | 2013-07-04 |
Family
ID=48697243
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/083070 WO2013099754A1 (ja) | 2011-12-26 | 2012-12-20 | 2-フルオロフェニルオキシメタン構造を持つ化合物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9079836B2 (ja) |
JP (1) | JP5382268B1 (ja) |
KR (1) | KR101488313B1 (ja) |
CN (1) | CN103717563B (ja) |
TW (1) | TWI518062B (ja) |
WO (1) | WO2013099754A1 (ja) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013172162A1 (ja) * | 2012-05-15 | 2013-11-21 | Dic株式会社 | 2-フルオロフェニルオキシメタン構造を持つ化合物 |
WO2015012156A1 (ja) * | 2013-07-25 | 2015-01-29 | Dic株式会社 | 2,6-ジフルオロフェニルエーテル構造を持つ液晶性化合物及びその液晶組成物 |
KR20150132588A (ko) * | 2013-10-03 | 2015-11-25 | 디아이씨 가부시끼가이샤 | 2,6-디플루오로페닐에테르 구조를 갖는 액정성 화합물 및 그 액정 조성물 |
US10000700B2 (en) | 2014-07-31 | 2018-06-19 | Dic Corporation | Nematic liquid crystal composition |
US10253258B2 (en) | 2014-07-31 | 2019-04-09 | Dic Corporation | Nematic liquid crystal composition |
US10544365B2 (en) | 2013-08-30 | 2020-01-28 | Dic Corporation | Nematic liquid crystal composition |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6085912B2 (ja) * | 2012-08-01 | 2017-03-01 | Dic株式会社 | 化合物、液晶組成物および液晶表示素子 |
JP5534381B1 (ja) | 2012-08-22 | 2014-06-25 | Dic株式会社 | ネマチック液晶組成物 |
WO2014034772A1 (ja) * | 2012-09-03 | 2014-03-06 | Dic株式会社 | ネマチック液晶組成物 |
CN112125788B (zh) * | 2020-10-19 | 2023-04-07 | 宁夏中星显示材料有限公司 | 一种含有二氟甲基醚桥键的液晶单体化合物的制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005529176A (ja) * | 2002-06-12 | 2005-09-29 | エフ.ホフマン−ラ ロシュ アーゲー | フルオロベンズアミド |
WO2009034867A1 (ja) * | 2007-09-10 | 2009-03-19 | Chisso Corporation | 液晶性化合物、液晶組成物および液晶表示素子 |
WO2012161178A1 (ja) * | 2011-05-26 | 2012-11-29 | Dic株式会社 | 2-フルオロフェニルオキシメタン構造を持つ化合物 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3732284A1 (de) | 1987-09-25 | 1989-04-13 | Merck Patent Gmbh | Substituierte phenyltrifluormethylether |
JP2696557B2 (ja) | 1989-03-07 | 1998-01-14 | チッソ株式会社 | トリフルオロベンゼン誘導体 |
DE4027840A1 (de) | 1989-09-06 | 1991-03-07 | Merck Patent Gmbh | Fluorbenzolderivate und fluessigkristallines medium |
BR9007097A (pt) | 1989-12-06 | 1992-02-18 | Merck Patent Gmbh | Compostos de 2,6-difluorbenzeno 1,4-dissubstituidos e meio cristalino liquido |
JP3823354B2 (ja) | 1995-12-05 | 2006-09-20 | チッソ株式会社 | 酸素原子含有結合基を持つアルケニル化合物、液晶組成物および液晶表示素子 |
JP2961650B2 (ja) | 1996-09-25 | 1999-10-12 | チッソ株式会社 | 置換ベンゼン誘導体、液晶組成物および液晶表示素子 |
JP4044618B2 (ja) | 1996-11-28 | 2008-02-06 | チッソ株式会社 | フッ素置換ベンゼン誘導体、液晶組成物および液晶表示素子 |
JP5152947B2 (ja) | 1999-06-15 | 2013-02-27 | Dic株式会社 | 2−フルオロナフタレン誘導体である新規液晶性化合物とそれを含有する液晶組成物 |
KR100977949B1 (ko) | 2002-02-05 | 2010-08-24 | 메르크 파텐트 게엠베하 | 액정 매질 및 액정 디스플레이 |
DE602004025254D1 (de) | 2003-08-25 | 2010-03-11 | Merck Patent Gmbh | Verbindungen zum einsatz in flüssigkristallinen medien |
JP2009292729A (ja) * | 2007-02-28 | 2009-12-17 | Chisso Corp | Cf2o結合基を有する5環液晶化合物、液晶組成物および液晶表示素子 |
EP2116522B1 (en) | 2007-02-28 | 2013-09-18 | JNC Corporation | Pentacyclic liquid crystal compound having cf<sb>2</sb>o bonding group, liquid crystal composition and liquid crystal display |
EP2351741B1 (en) * | 2008-10-21 | 2016-11-30 | JNC Corporation | Pentacyclic liquid crystal compound having nitrogen-containing heterocyclic ring, liquid crystal composition, and liquid crystal display device |
-
2012
- 2012-12-03 TW TW101145223A patent/TWI518062B/zh not_active IP Right Cessation
- 2012-12-20 JP JP2013526263A patent/JP5382268B1/ja not_active Expired - Fee Related
- 2012-12-20 WO PCT/JP2012/083070 patent/WO2013099754A1/ja active Application Filing
- 2012-12-20 CN CN201280036957.0A patent/CN103717563B/zh active Active
- 2012-12-20 US US14/346,498 patent/US9079836B2/en not_active Expired - Fee Related
- 2012-12-20 KR KR20137031494A patent/KR101488313B1/ko active IP Right Grant
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005529176A (ja) * | 2002-06-12 | 2005-09-29 | エフ.ホフマン−ラ ロシュ アーゲー | フルオロベンズアミド |
WO2009034867A1 (ja) * | 2007-09-10 | 2009-03-19 | Chisso Corporation | 液晶性化合物、液晶組成物および液晶表示素子 |
WO2012161178A1 (ja) * | 2011-05-26 | 2012-11-29 | Dic株式会社 | 2-フルオロフェニルオキシメタン構造を持つ化合物 |
Non-Patent Citations (2)
Title |
---|
DATABASE REGISTRY CAS; 3 October 2011 (2011-10-03), accession no. 334226-61-7 * |
M.KUCHAR ET AL.: "USE OF QSAR IN DESIGN OF ANTIINFLAMMATORY FLUORINATED ARYLALKANOIC ACIDS", COLLECTION OF CZECHOSLOVAK CHEMICAL COMMUNICATIONS, vol. 55, no. 1, 1990, pages 296 - 306, XP001002035 * |
Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2013172162A1 (ja) * | 2012-05-15 | 2013-11-21 | Dic株式会社 | 2-フルオロフェニルオキシメタン構造を持つ化合物 |
US9181484B2 (en) | 2012-05-15 | 2015-11-10 | Dic Corporation | Compound having 2-fluorophenyloxymethane structure |
WO2015012156A1 (ja) * | 2013-07-25 | 2015-01-29 | Dic株式会社 | 2,6-ジフルオロフェニルエーテル構造を持つ液晶性化合物及びその液晶組成物 |
CN105308028A (zh) * | 2013-07-25 | 2016-02-03 | Dic株式会社 | 具有2,6-二氟苯醚结构的液晶性化合物及其液晶组合物 |
KR101613602B1 (ko) | 2013-07-25 | 2016-04-19 | 디아이씨 가부시끼가이샤 | 2,6-디플루오로페닐에테르 구조를 갖는 액정성 화합물 및 그 액정 조성물 |
US9637466B2 (en) | 2013-07-25 | 2017-05-02 | Dic Corporation | Liquid crystal compound having 2, 6-difluorophenyl ether structure and liquid crystal composition thereof |
US10544365B2 (en) | 2013-08-30 | 2020-01-28 | Dic Corporation | Nematic liquid crystal composition |
KR20150132588A (ko) * | 2013-10-03 | 2015-11-25 | 디아이씨 가부시끼가이샤 | 2,6-디플루오로페닐에테르 구조를 갖는 액정성 화합물 및 그 액정 조성물 |
KR101649180B1 (ko) | 2013-10-03 | 2016-08-19 | 디아이씨 가부시끼가이샤 | 2,6-디플루오로페닐에테르 구조를 갖는 액정성 화합물 및 그 액정 조성물 |
US9573923B2 (en) | 2013-10-03 | 2017-02-21 | Dic Corporation | Liquid crystal compound having 2, 6-difluorophenylether structure, and liquid crystal composition containing the same |
US10000700B2 (en) | 2014-07-31 | 2018-06-19 | Dic Corporation | Nematic liquid crystal composition |
US10253258B2 (en) | 2014-07-31 | 2019-04-09 | Dic Corporation | Nematic liquid crystal composition |
Also Published As
Publication number | Publication date |
---|---|
US9079836B2 (en) | 2015-07-14 |
KR101488313B1 (ko) | 2015-01-30 |
US20140330045A1 (en) | 2014-11-06 |
TWI518062B (zh) | 2016-01-21 |
TW201331174A (zh) | 2013-08-01 |
JP5382268B1 (ja) | 2014-01-08 |
CN103717563A (zh) | 2014-04-09 |
CN103717563B (zh) | 2015-09-16 |
JPWO2013099754A1 (ja) | 2015-05-07 |
KR20130138859A (ko) | 2013-12-19 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5382268B1 (ja) | 2−フルオロフェニルオキシメタン構造を持つ化合物 | |
JP5263461B2 (ja) | 2−フルオロフェニルオキシメタン構造を持つ化合物 | |
JP5435318B1 (ja) | 2−フルオロフェニルオキシメタン構造を持つ化合物 | |
JP6137419B2 (ja) | ネマチック液晶組成物及びこれを用いた液晶表示素子 | |
JP4876420B2 (ja) | ジフルオロベンゼン誘導体 | |
US8003006B2 (en) | Difluorobenzene derivative and nematic liquid crystal composition using the same | |
JP6070110B2 (ja) | フッ素化ナフタレン構造を持つ化合物 | |
JP5622066B2 (ja) | フッ素化ナフタレン構造を持つ化合物及びその液晶組成物 | |
JP4887605B2 (ja) | クロマン誘導体及びこの化合物を含有する液晶組成物 | |
JP2013001683A (ja) | 2,6,7−トリオキサ−ビシクロ[2.2.2]オクタン骨格を持つ液晶化合物及び液晶組成物 | |
JP6085912B2 (ja) | 化合物、液晶組成物および液晶表示素子 | |
JP4835032B2 (ja) | トリフルオロナフタレン誘導体 | |
JP5962992B2 (ja) | フッ素化ナフタレン構造を持つ化合物 | |
TWI650311B (zh) | 含有亞乙氧基的化合物及其組合物和應用 | |
JP4501388B2 (ja) | ジフルオロテトラヒドロナフタレン誘導体を含有する液晶組成物及び液晶性化合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013526263 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12861775 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20137031494 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14346498 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 12861775 Country of ref document: EP Kind code of ref document: A1 |