JP2007277127A - Halogen-containing compound, liquid crystal composition and electrooptical display element - Google Patents
Halogen-containing compound, liquid crystal composition and electrooptical display element Download PDFInfo
- Publication number
- JP2007277127A JP2007277127A JP2006103672A JP2006103672A JP2007277127A JP 2007277127 A JP2007277127 A JP 2007277127A JP 2006103672 A JP2006103672 A JP 2006103672A JP 2006103672 A JP2006103672 A JP 2006103672A JP 2007277127 A JP2007277127 A JP 2007277127A
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- Prior art keywords
- liquid crystal
- general formula
- halogen
- compound
- mmol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 80
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 63
- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 229910052736 halogen Inorganic materials 0.000 title claims abstract description 27
- 150000002367 halogens Chemical class 0.000 title claims abstract description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 17
- 125000005843 halogen group Chemical group 0.000 claims description 12
- 229910052731 fluorine Inorganic materials 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 9
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 125000002947 alkylene group Chemical group 0.000 claims description 7
- 210000002858 crystal cell Anatomy 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 abstract description 6
- 239000004988 Nematic liquid crystal Substances 0.000 abstract description 5
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 abstract description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 57
- -1 Nitrile compounds Chemical class 0.000 description 55
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 27
- 239000012071 phase Substances 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 19
- 238000006243 chemical reaction Methods 0.000 description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000002904 solvent Substances 0.000 description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- 239000000741 silica gel Substances 0.000 description 14
- 229910002027 silica gel Inorganic materials 0.000 description 14
- 239000007788 liquid Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 238000005160 1H NMR spectroscopy Methods 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000000926 separation method Methods 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- 238000000862 absorption spectrum Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 125000003709 fluoroalkyl group Chemical group 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 6
- AXTNQJKYTXEYRM-UHFFFAOYSA-N 1,3-difluoro-5-propylbenzene Chemical compound CCCC1=CC(F)=CC(F)=C1 AXTNQJKYTXEYRM-UHFFFAOYSA-N 0.000 description 5
- 125000003545 alkoxy group Chemical group 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000001308 synthesis method Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000003098 cholesteric effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 4
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- UWCWUCKPEYNDNV-LBPRGKRZSA-N 2,6-dimethyl-n-[[(2s)-pyrrolidin-2-yl]methyl]aniline Chemical compound CC1=CC=CC(C)=C1NC[C@H]1NCCC1 UWCWUCKPEYNDNV-LBPRGKRZSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 3
- 229940071870 hydroiodic acid Drugs 0.000 description 3
- 150000002440 hydroxy compounds Chemical class 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- RXYPXQSKLGGKOL-UHFFFAOYSA-N 1,4-dimethylpiperazine Chemical compound CN1CCN(C)CC1 RXYPXQSKLGGKOL-UHFFFAOYSA-N 0.000 description 2
- DCTOHCCUXLBQMS-UHFFFAOYSA-N 1-undecene Chemical compound CCCCCCCCCC=C DCTOHCCUXLBQMS-UHFFFAOYSA-N 0.000 description 2
- AHDSRXYHVZECER-UHFFFAOYSA-N 2,4,6-tris[(dimethylamino)methyl]phenol Chemical compound CN(C)CC1=CC(CN(C)C)=C(O)C(CN(C)C)=C1 AHDSRXYHVZECER-UHFFFAOYSA-N 0.000 description 2
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 2
- 0 C*(*)C1CC(*)C(*C(C)(C)c2cc(*)c(*c(cc3*)c(C)c(*)c3O)c(*)c2)C(*)C1 Chemical compound C*(*)C1CC(*)C(*C(C)(C)c2cc(*)c(*c(cc3*)c(C)c(*)c3O)c(*)c2)C(*)C1 0.000 description 2
- 101150065749 Churc1 gene Proteins 0.000 description 2
- 102100038239 Protein Churchill Human genes 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000003302 alkenyloxy group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 125000004104 aryloxy group Chemical group 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- AZSZCFSOHXEJQE-UHFFFAOYSA-N dibromodifluoromethane Chemical compound FC(F)(Br)Br AZSZCFSOHXEJQE-UHFFFAOYSA-N 0.000 description 2
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 125000005004 perfluoroethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 2
- 125000005009 perfluoropropyl group Chemical group FC(C(C(F)(F)F)(F)F)(F)* 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 2
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical compound C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- AMSVWDFSTNMNTP-UHFFFAOYSA-N 1-(difluoromethyl)-2-phenylbenzene Chemical group FC(F)C1=CC=CC=C1C1=CC=CC=C1 AMSVWDFSTNMNTP-UHFFFAOYSA-N 0.000 description 1
- 125000004206 2,2,2-trifluoroethyl group Chemical group [H]C([H])(*)C(F)(F)F 0.000 description 1
- 125000004959 2,6-naphthylene group Chemical group [H]C1=C([H])C2=C([H])C([*:1])=C([H])C([H])=C2C([H])=C1[*:2] 0.000 description 1
- FUIQBJHUESBZNU-UHFFFAOYSA-N 2-[(dimethylazaniumyl)methyl]phenolate Chemical compound CN(C)CC1=CC=CC=C1O FUIQBJHUESBZNU-UHFFFAOYSA-N 0.000 description 1
- AECMQTCXISKOGO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethyl]phenol Chemical compound CN(C)CCC1=CC=CC=C1O AECMQTCXISKOGO-UHFFFAOYSA-N 0.000 description 1
- 125000005916 2-methylpentyl group Chemical group 0.000 description 1
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000005917 3-methylpentyl group Chemical group 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 241001483078 Phyto Species 0.000 description 1
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000004423 acyloxy group Chemical group 0.000 description 1
- 125000004183 alkoxy alkyl group Chemical group 0.000 description 1
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 1
- 125000000304 alkynyl group Chemical group 0.000 description 1
- 125000005133 alkynyloxy group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 125000005199 aryl carbonyloxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000000480 butynyl group Chemical group [*]C#CC([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000000596 cyclohexenyl group Chemical group C1(=CCCCC1)* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000004807 desolvation Methods 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000005678 ethenylene group Chemical group [H]C([*:1])=C([H])[*:2] 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000005448 ethoxyethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])C([H])([H])* 0.000 description 1
- 125000005745 ethoxymethyl group Chemical group [H]C([H])([H])C([H])([H])OC([H])([H])* 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 description 1
- 229910000103 lithium hydride Inorganic materials 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 150000004681 metal hydrides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000004184 methoxymethyl group Chemical group [H]C([H])([H])OC([H])([H])* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 description 1
- ZUHZZVMEUAUWHY-UHFFFAOYSA-N n,n-dimethylpropan-1-amine Chemical compound CCCN(C)C ZUHZZVMEUAUWHY-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000005767 propoxymethyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])[#8]C([H])([H])* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002568 propynyl group Chemical group [*]C#CC([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000714 pyrimidinyl group Chemical group 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000012312 sodium hydride Substances 0.000 description 1
- 229910000104 sodium hydride Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 1
- 125000000725 trifluoropropyl group Chemical group [H]C([H])(*)C([H])([H])C(F)(F)F 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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- Liquid Crystal (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
Description
本発明は、含ハロゲン化合物に関するものである。また、該含ハロゲン化合物を含有する液晶組成物に関するものである。さらに液晶セルに該液晶組成物を封入してなる電気光学表示素子に関するものである。 The present invention relates to a halogen-containing compound. The present invention also relates to a liquid crystal composition containing the halogen-containing compound. Further, the present invention relates to an electro-optic display element in which the liquid crystal composition is sealed in a liquid crystal cell.
液晶化合物の特性である光学（屈折率）異方性（Δｎ）や誘電率異方性（Δε）を利用した液晶表示素子はこれまで多数作られており、時計を始め電卓、各種測定機器、自動車用パネル、ワープロ、電子手帳、携帯電話、プリンタ−、コンピュ−タ−、テレビ等に広く利用され、需要も年々高くなってきている。液晶化合物には個体相と液体相の中間に位置する固有の液晶相があり、その相形態はネマチック相、スメクチック相及びコレステリック相に大別されるが、そのうち表示素子用にはネマチック相が現在最も広く利用されている。また、液晶表示に応用されている方式のうち、表示方式としてはこれまでに多数のものが提案されており、例えば動的散乱型（ＤＳ型）、ゲスト・ホスト型（ＧＨ型）、ねじれネマチック型（ＴＮ型）、超ねじれネマチック型（ＳＴＮ型）、薄膜トランジスター型（ＴＦＴ型）及び強誘電性液晶（ＦＬＣ）等が知られており、駆動方式としてはスタティック駆動方式、時分割駆動方式、アクティブマトリックス駆動方式及び２周波駆動方式等が知られている。 Many liquid crystal display elements using optical (refractive index) anisotropy (Δn) and dielectric anisotropy (Δε), which are the characteristics of liquid crystal compounds, have been made so far, including watches, calculators, various measuring instruments, Widely used in automobile panels, word processors, electronic notebooks, mobile phones, printers, computers, televisions, and the like, the demand is increasing year by year. A liquid crystal compound has an intrinsic liquid crystal phase located between the solid phase and the liquid phase, and the phase morphology is roughly divided into a nematic phase, a smectic phase, and a cholesteric phase. Among them, the nematic phase is currently used for display elements. Most widely used. Also, among the methods applied to liquid crystal displays, many display methods have been proposed so far, such as dynamic scattering type (DS type), guest-host type (GH type), and twisted nematic. Type (TN type), super twisted nematic type (STN type), thin film transistor type (TFT type), ferroelectric liquid crystal (FLC), etc. are known. As a driving method, a static driving method, a time division driving method, An active matrix driving method and a two-frequency driving method are known.
一般に誘電率の異方性（Δε）（以下単に「Δε」ということがある）が正の液晶組成物を用いる電界効果型液晶表示装置のしきい値電圧は、組成物のΔεの平方根に反比例することが知られている。特に近年、ツイストネマチック（ＴＮ）液晶素子はバッテリー駆動式が主流になり、特にしきい値の低い液晶材料が要求されており、そのためには、大きな正のΔεを有する液晶材料が重要になる。 In general, the threshold voltage of a field effect liquid crystal display device using a liquid crystal composition having a positive dielectric anisotropy (Δε) (hereinafter sometimes simply referred to as “Δε”) is inversely proportional to the square root of Δε of the composition. It is known to do. In recent years, in particular, twisted nematic (TN) liquid crystal elements have become battery-driven, and liquid crystal materials having a particularly low threshold are required. For this purpose, liquid crystal materials having a large positive Δε are important.
４−（ｐ−アルキルシクロヘキシル）ベンゾニトリル等のニトリル化合物は大きなΔεを有することからＴＮ液晶素子あるいはスーパーツイストネマチック（ＳＴＮ）素子用の液晶材料として用いられていた。しかしながら、これらのニトリル化合物はイオン性の不純物を抱き込みやすいため、高い抵抗率（１０12Ωｃｍ以上）の要求されるアクティブマトリックス駆動には用いることができなかった。そのため、高い抵抗率を有し、Δεの大きな液晶材料が求められている。 Nitrile compounds such as 4- (p-alkylcyclohexyl) benzonitrile have been used as liquid crystal materials for TN liquid crystal elements or super twist nematic (STN) elements because of their large Δε. However, since these nitrile compounds are easy to incorporate ionic impurities, they cannot be used for active matrix driving that requires high resistivity (10 12 Ωcm or more). Therefore, a liquid crystal material having a high resistivity and a large Δε is demanded.
また、液晶組成物の粘度は液晶の応答速度に対し影響し、低粘度のもの程その応答が速い。従って、液晶組成物の配合剤としては、低粘度であるものが好ましい。 The viscosity of the liquid crystal composition affects the response speed of the liquid crystal, and the lower the viscosity, the faster the response. Therefore, the compounding agent for the liquid crystal composition preferably has a low viscosity.
また、ＮＩ点は、液晶状態を示す温度範囲に影響するもので、ＮＩ点が高くなると高温においても液晶状態を示すことになる。 The NI point affects the temperature range indicating the liquid crystal state. When the NI point is increased, the liquid crystal state is exhibited even at a high temperature.
末端基としてフルオロアルキル（オキシ）基を有する化合物が正の誘電異方性を有し、かつイオン性不純物を含みにくいため、特に、アクティブマトリックス駆動方式に求められる、高低効率、高い電圧保持率（ＶＨＲ）、低いイオン密度などを発現する液晶材料として知られており、これまでにもフルオロアルキル（オキシ）基を導入することが試みられており、例えば、特開昭５５−７２１４３号公報、特開昭５５−４０６６０号公報、特開昭６１−１９７５６３号公報、特開昭５６−１２３２２号公報、特開昭５８−１５４５３２号公報、特開昭５８−１７７９３９号公報、特開昭５８−２１００４５号公報、特開昭５９−７８１２９号公報、特表平６−５００３４３号公報等には、フルオロアルキル基を有する化合物が種種提案されており、また、特表平１−５０３１４５号公報には、フルオロアルキル基を有する化合物を使用した電気光学表示素子が提案されており、さらに、特表平３−５０２９４２号公報、特開平１０−６７９８９号公報などには、フロオロアルキル（オキシ）基を有する化合物などを使用したアクティブマトリックス液晶表示体が提案されている。
しかしながら、これらに具体的に記載されているフルオロアルキル基を有する化合物では、低粘度、幅広いネマチック相を有するという点において未だ満足できるものではなかった。
A compound having a fluoroalkyl (oxy) group as a terminal group has a positive dielectric anisotropy and hardly contains an ionic impurity. Therefore, the high and low efficiency and high voltage holding ratio (especially required for an active matrix driving method) VHR) is known as a liquid crystal material that expresses a low ion density, and attempts have been made to introduce a fluoroalkyl (oxy) group so far. For example, JP-A-55-72143, JP 55-40660, JP 61-197563, JP 56-12322, JP 58-154532, JP 58-177939, JP 58-210045. No. 5, JP-A-59-78129, JP-A-6-500343 and the like have proposed various compounds having a fluoroalkyl group. JP-A-1-503145 proposes an electro-optic display element using a compound having a fluoroalkyl group. Further, JP-A-3-5032942 and JP-A-10-67989 are proposed. Japanese Laid-Open Patent Publication No. 2000-228, etc. proposes an active matrix liquid crystal display using a compound having a fluoroalkyl (oxy) group.
However, the compounds having a fluoroalkyl group specifically described therein have not yet been satisfactory in that they have a low viscosity and a wide nematic phase.
また、国際公開２００４／０５８６７６号公報には、パーフルオロアルキルオキシ化合物が提案されているが、ここに具体的に記載された化合物では、狭セルでの高速応答性や低電圧駆動といった要求に十分に満足できるような、高い液晶上限温度（ＮＩ点）を有しながら、高い屈折率の異方性（Δｎ）、高い誘電率の異方性（Δε）を有する材料が提供できていないという欠点があった。 Further, perfluoroalkyloxy compounds have been proposed in International Publication No. 2004/058676, but the compounds specifically described here are sufficient for demands such as high-speed response in a narrow cell and low voltage drive. However, it is not possible to provide a material having a high liquid crystal anisotropy (Δn) and a high dielectric constant anisotropy (Δε) while having a high liquid crystal upper limit temperature (NI point) that satisfies the above requirement. was there.
従って、本発明の目的は、ネマチック液晶材料に混合して、低粘度で、高い屈折率の異方性（Δｎ）、高い誘電率の異方性（Δε）および高ＮＩ点（幅広いネマチック相）を有する液晶組成物を形成し得る新規液晶材料を提供することにある。 Therefore, the object of the present invention is to mix a nematic liquid crystal material with low viscosity, high refractive index anisotropy (Δn), high dielectric constant anisotropy (Δε) and high NI point (wide nematic phase). It is an object to provide a novel liquid crystal material capable of forming a liquid crystal composition having the following.
本発明者らは、鋭意検討を行った結果、ラテラル位にハロゲン原子を有する特定の含ハロゲン化合物が、ネマチック液晶組成物に配合することで液晶温度範囲を狭めることなく、高いΔε及び高いΔｎを提供することのできる材料あることを見出し、本発明に到達した。 As a result of intensive investigations, the present inventors have found that a specific halogen-containing compound having a halogen atom at a lateral position has a high Δε and a high Δn without narrowing the liquid crystal temperature range by blending into a nematic liquid crystal composition. The inventors have found that there are materials that can be provided, and have reached the present invention.
即ち、本発明は、上記知見に基づきなされたもので、下記一般式（Ｉ）で表されることを特徴とする含ハロゲン化合物を提供することで、上記目的を達成したものである。 That is, the present invention has been made based on the above findings, and has achieved the above object by providing a halogen-containing compound represented by the following general formula (I).
また、本発明は、下記一般式（Ｉ−１）で表されることを特徴とする含ハロゲン化合物を提供することで、上記目的を達成したものである。 Moreover, this invention achieves the said objective by providing the halogen-containing compound characterized by being represented with the following general formula (I-1).
また、本発明は、下記一般式（Ｉ−２）で表されることを特徴とする含ハロゲン化合物を提供することで、上記目的を達成したものである。 Moreover, this invention achieves the said objective by providing the halogen-containing compound represented by the following general formula (I-2).
また、本発明は、下記一般式（Ｉ−２（ａ））で表されることを特徴とする含ハロゲン化合物を提供することで、上記目的を達成したものである。 Moreover, this invention achieves the said objective by providing the halogen-containing compound characterized by being represented with the following general formula (I-2 (a)).
また、本発明は、下記一般式（Ｉ−２（ｂ））で表されることを特徴とする含ハロゲン化合物を提供することで、上記目的を達成したものである。 Moreover, this invention achieves the said objective by providing the halogen-containing compound characterized by being represented by the following general formula (I-2 (b)).
また、本発明は、上記含ハロゲン化合物を含有する液晶組成物を提供することで、上記目的を達成したものである。 Moreover, this invention achieves the said objective by providing the liquid crystal composition containing the said halogen-containing compound.
また、本発明は、液晶セルに上記液晶組成物を封入してなる電気光学表示素子を提供することで、上記目的を達成したものである。 In addition, the present invention achieves the above object by providing an electro-optic display device in which the liquid crystal composition is sealed in a liquid crystal cell.
本発明の含ハロゲン化合物は、ネマチック液晶組成物に配合することで液晶温度範囲を狭めることなく、高いΔε、高いΔｎを提供することのできるであり、本発明の含ハロゲン化合物を含有して得られる液晶組成物は、あらゆる表示方式およびあらゆる駆動方式の電気光学素子用の液晶材料として有用なものである。 The halogen-containing compound of the present invention can provide high Δε and high Δn without narrowing the liquid crystal temperature range by blending with the nematic liquid crystal composition, and is obtained by containing the halogen-containing compound of the present invention. The obtained liquid crystal composition is useful as a liquid crystal material for electro-optic elements of all display systems and all drive systems.
以下、本発明の含ハロゲン化合物、液晶組成物及び電気光学表示素子について、好ましい実施形態に基づき詳細に説明する。 Hereinafter, the halogen-containing compound, the liquid crystal composition, and the electro-optic display device of the present invention will be described in detail based on preferred embodiments.
前記一般式（Ｉ）において、Ｒ1は、Ｒ0、Ｒ0Ｏ、Ｒ0ＯＣＯ又はＲ0ＣＯＯを表し、Ｒ0で表されるアルキル基としては、例えば、メチル、エチル、プロピル、ブチル、ペンチル、ヘキシル、ヘプチル、オクチル、ノニル、デシル、ビニル、アリル、ブテニル、エチニル、プロピニル、ブチニル、メトキシメチル、エトキシメチル、プロポキシメチル、ブトキシメチル、メトキシエチル、エトキシエチル、パーフルオロメチル、パーフルオロエチル、パーフルオロプロピル、モノフルオロメチル、ジフルオロメチル、２，２，２−トリフルオロメチル、パーフルオロビニル、パーフルオロアリル、イソプロピル、１−メチルプロピル、２−メチルプロピル、２−ブチルメチル、３−メチルブチル、２−メチルペンチル、３−メチルペンチル、２−エチルヘキシル、２−プロピルペンチル、１−メチルペンチルなどがあげられる。 In the general formula (I), R 1 represents R 0 , R 0 O, R 0 OCO or R 0 COO, and examples of the alkyl group represented by R 0 include methyl, ethyl, propyl, butyl, Pentyl, hexyl, heptyl, octyl, nonyl, decyl, vinyl, allyl, butenyl, ethynyl, propynyl, butynyl, methoxymethyl, ethoxymethyl, propoxymethyl, butoxymethyl, methoxyethyl, ethoxyethyl, perfluoromethyl, perfluoroethyl, Perfluoropropyl, monofluoromethyl, difluoromethyl, 2,2,2-trifluoromethyl, perfluorovinyl, perfluoroallyl, isopropyl, 1-methylpropyl, 2-methylpropyl, 2-butylmethyl, 3-methylbutyl, 2 -Methylpentyl, 3-methylpentyl , 2-ethylhexyl, 2-propylpentyl, 1-methylpentyl and the like.
前記一般式（Ｉ）のＡ1の具体例としては、１，４−フェニレン、２−フルオロ−１，４−フェニレン、３−フルオロ−１，４−フェニレン、３，５−ジフルオロ−１，４−フェニレン、３−クロロ−１，４−フェニレン、３−シアノ−１，４−フェニレン、ピリジン−２，５−ジイル、ピリミジン−２，５−ジイル、ピラゾリン−２，５−ジイル、ピリダジン−２，５−ジイル、１，４−シクロへキシレン、テトラヒドロピラン−２，５−ジイル、ジオキサン−２，５−ジイル、ジチオキサン−２，５−ジイル２，６−ナフチレン、テトラヒドロナフタレン−２，６−ジイル、デカヒドロナフタレン−２，６−ジイルなどがあげられる。 Specific examples of A 1 in the general formula (I) include 1,4-phenylene, 2-fluoro-1,4-phenylene, 3-fluoro-1,4-phenylene, 3,5-difluoro-1,4. -Phenylene, 3-chloro-1,4-phenylene, 3-cyano-1,4-phenylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, pyrazoline-2,5-diyl, pyridazine-2 , 5-diyl, 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, dioxane-2,5-diyl, dithioxan-2,5-diyl 2,6-naphthylene, tetrahydronaphthalene-2,6- Examples thereof include diyl and decahydronaphthalene-2,6-diyl.
前記一般式（Ｉ）において、Ｙで表されるハロゲン化されたアルキル基としては、モノフルオロメチル、ジフルオロメチル、トリフルオロメチル、２−モノフルオロエチル、２，２，２−トリフルオロエチル、１，２，２−トリフルオロエチル、パーフルオロエチル、モノフルオロプロピル、ジフルオロプロピル、トリフルオロプロピル、パーフルオロプロピル等があげられ、ハロゲン化されたアルケニル基としては、モノフルオロビニル、ジフルオロビニル、パーフルオロビニル、トリフルオロアリル、パーフルオロアリル、パーフルオロアリルオキシメチル、パーフルオロアリルオキシモノフルオロメチルが等があげられ、ハロゲン化されたアルコキシ基としては、モノフルオロメトキシ、ジフルオロメトキシ、トリフルオロメトキシ、２−モノフルオロエトキシ、２，２，２−トリフルオロエトキシ、１，２，２−トリフルオロエトキシ、パーフルオロエトキシ、モノフルオロプロピルオキシ、ジフルオロプロピルオキシ、トリフルオロプロピルオキシ、パーフルオロプロピルオキシ等があげられ、ハロゲン化されたアルケニルオキシ基としては、モノフルオロビニルオキシ、ジフルオロビニルオキシ、パーフルオロビニルオキシ、トリフルオロアリルオキシ、パーフルオロアリルオキシがあげられる。これらの中でも、Ｙが下記一般式（ＩＩ）で表される基が好ましい。 In the general formula (I), examples of the halogenated alkyl group represented by Y include monofluoromethyl, difluoromethyl, trifluoromethyl, 2-monofluoroethyl, 2,2,2-trifluoroethyl, 1 2,2-trifluoroethyl, perfluoroethyl, monofluoropropyl, difluoropropyl, trifluoropropyl, perfluoropropyl, etc., and halogenated alkenyl groups include monofluorovinyl, difluorovinyl, perfluoro Vinyl, trifluoroallyl, perfluoroallyl, perfluoroallyloxymethyl, perfluoroallyloxymonofluoromethyl, etc., and halogenated alkoxy groups include monofluoromethoxy, difluoromethoxy, trifluoromethoxy, -Monofluoroethoxy, 2,2,2-trifluoroethoxy, 1,2,2-trifluoroethoxy, perfluoroethoxy, monofluoropropyloxy, difluoropropyloxy, trifluoropropyloxy, perfluoropropyloxy, etc. Examples of the halogenated alkenyloxy group include monofluorovinyloxy, difluorovinyloxy, perfluorovinyloxy, trifluoroallyloxy, and perfluoroallyloxy. Among these, Y is preferably a group represented by the following general formula (II).
また、前記一般式(ＩＩ)において、Ｂで表されるアルキレン基としては、メチレン、モノフルオロメチレン、ジフルオロメチレン、エチレン、モノフルオロエチレン、ジフルオロエチレン、トリフルオロエチレン、パーフルオロエチレンが挙げられる。 In the general formula (II), examples of the alkylene group represented by B include methylene, monofluoromethylene, difluoromethylene, ethylene, monofluoroethylene, difluoroethylene, trifluoroethylene, and perfluoroethylene.
本発明の前記一般式（Ｉ）として表される化合物の具体例としては、下記化合物などがあげられるが、これらの化合物に限定されるものではない。尚、Ｒ1は前記一般式（Ｉ）におけるＲ1と同様である。 Specific examples of the compound represented by the general formula (I) of the present invention include the following compounds, but are not limited to these compounds. Incidentally, R 1 is the same as R 1 in the general formula (I).
これらの化合物の中でも、下記一般式（Ｉ−１）で表される化合物は、上限温度を下げることなく、高いΔｎと高いΔεを提供しうる化合物であるため好ましい。 Among these compounds, a compound represented by the following general formula (I-1) is preferable because it can provide high Δn and high Δε without lowering the maximum temperature.
また、これらの化合物の中でも、下記一般式（Ｉ−２）で表される化合物は、上限温度を下げることなく、高いΔｎと高いΔεを提供しうる化合物であるため好ましい。 Among these compounds, a compound represented by the following general formula (I-2) is preferable because it can provide high Δn and high Δε without lowering the maximum temperature.
また、これらの化合物の中でも、下記一般式（Ｉ−２（ａ））に該当する化合物は、上限温度を下げることなく、高いΔｎと高いΔεを提供しうる化合物であるため好ましい。 Among these compounds, compounds corresponding to the following general formula (I-2 (a)) are preferable because they can provide high Δn and high Δε without lowering the maximum temperature.
また、これらの化合物の中でも、下記一般式（Ｉ−２（ｂ））に該当する化合物は、低回転粘性係数（γ1）を有し、高いΔεを提供しうる化合物であるため好ましい。 Among these compounds, compounds corresponding to the following general formula (I-2 (b)) are preferable because they have a low rotational viscosity coefficient (γ 1 ) and can provide a high Δε.
本発明の含ハロゲン化合物は、その製造方法によって制限を受けるものではないが、例えば本発明の含ハロゲン化合物は、その製造方法によって制限を受けるものではないが、例えば、Ｙが、−ＯＣＦ2ＣＦ＝ＣＦ2である化合物は、下記反応式に従って製造することができる。これ以外の化合物についてもこれに順ずる方法によって製造することができる。
尚、下記パーフルオロ化合物におけるＸは、ヨウ素原子、臭素原子、モノフルオロスルホン酸等を表す。
The halogen-containing compound of the present invention is not limited by the production method. For example, the halogen-containing compound of the present invention is not limited by the production method. For example, Y is —OCF 2 CF. = CF 2 can be produced according to the following reaction formula. Other compounds can also be produced by a method according to this.
In the following perfluoro compound, X represents an iodine atom, a bromine atom, monofluorosulfonic acid or the like.
ここで、上記反応に使用される塩基（BASE）としては、水酸化ナトリウム、水酸化カリウム等の金属酸化物；水素化リチウム、水素化ナトリウム等の金属水素化物；トリエチルアミン、エチルジメチルアミン、プロピルジメチルアミン、Ｎ，Ｎ´−ジメチルピペラジン、ピリジン、ピコリン、１，８−ジアザビスシクロ（５．４．０）ウンデセン−１（ＤＢＵ）、ベンジルジメチルアミン、２−（ジメチルアミノエチル）フェノール（ＤＭＰ−１０）、２，４，６−トリス（ジメチルアミノメチル）フェノール（ＤＭＰ−３０）等のアミン等が挙げられる。
また、上記反応に使用される溶媒（solv.）としては、トルエン、Ｎ，Ｎ−ジメチルホ
ルムアミド（ＤＭＦ）、１，３−ジメチルイミダゾリジノン（ＤＭＩ）、テトラヒドロフラン（ＴＨＦ）、トリエチルアミン等が挙げられる。
上記〔化２０〕の反応式中に示されるヒドロキシ化合物及びパーフルオロ化合物の使用量は、質量比（前者／後者）で好ましくは２０／１〜１／２０、さらに好ましくは１／１〜１／１０の範囲である。
上記塩基の使用量は、ヒドロキシ化合物に対して、好ましくは０．１〜５．０モル％、さらに好ましくは１．０〜２．０モル％である。
上記溶媒の使用量は、任意の量とすることができるが、好ましくは、ヒドロキシ化合物とパーフルオロ化合物との総量１００質量部に対して、１０〜５００質量部の範囲で適宜使用する。
Here, as the base (BASE) used in the above reaction, metal oxides such as sodium hydroxide and potassium hydroxide; metal hydrides such as lithium hydride and sodium hydride; triethylamine, ethyldimethylamine, propyldimethyl Amine, N, N′-dimethylpiperazine, pyridine, picoline, 1,8-diazabiscyclo (5.4.0) undecene-1 (DBU), benzyldimethylamine, 2- (dimethylaminoethyl) phenol (DMP-10) And amines such as 2,4,6-tris (dimethylaminomethyl) phenol (DMP-30).
Examples of the solvent (solv.) Used in the above reaction include toluene, N, N-dimethylformamide (DMF), 1,3-dimethylimidazolidinone (DMI), tetrahydrofuran (THF), triethylamine and the like. .
The use amount of the hydroxy compound and the perfluoro compound shown in the reaction formula of [Chemical Formula 20] is preferably 20/1 to 1/20, more preferably 1/1 to 1/1 / by mass ratio (the former / the latter). The range is 10.
The usage-amount of the said base becomes like this. Preferably it is 0.1-5.0 mol% with respect to a hydroxy compound, More preferably, it is 1.0-2.0 mol%.
The amount of the solvent used may be any amount, but is preferably used in the range of 10 to 500 parts by mass with respect to 100 parts by mass of the total amount of the hydroxy compound and the perfluoro compound.
本発明の含ハロゲン化合物は、液晶化合物として有用なものであり、従来既知の液晶化合物もしくは液晶類似化合物、またはそれらの混合物（母液晶）を配合することによって液晶組成物を構成するものである。
上記母液晶としては、例えば、下記一般式（ＩＩＩ）で表される化合物またはこれらの混合物があげられる。
また、本発明の含ハロゲン化合物の上記液晶組成物中の含有量は、1〜５０質量％が好ましく、３〜３０質量％がより好ましい。
The halogen-containing compound of the present invention is useful as a liquid crystal compound, and constitutes a liquid crystal composition by blending a conventionally known liquid crystal compound or liquid crystal similar compound, or a mixture thereof (mother liquid crystal).
Examples of the mother liquid crystal include a compound represented by the following general formula (III) or a mixture thereof.
Moreover, 1-50 mass% is preferable and, as for content in the said liquid-crystal composition of the halogen-containing compound of this invention, 3-30 mass% is more preferable.
上記一般式（ＩＩＩ）で表される化合物の具体例としては、下記の各化合物などがあげられる。尚、各化合物におけるＲ、Ｙ1、Ｙ2、Ｙ3およびＹ4は、上記一般式（Ｉ）におけるものと同じ意味である。 Specific examples of the compound represented by the general formula (III) include the following compounds. In addition, R, Y 1 , Y 2 , Y 3 and Y 4 in each compound have the same meaning as in the above general formula (I).
また、本発明の液晶組成物には、公知のカイラル剤を併用することができる。カイラル剤としては、例えば、下記の一般式（ＩＶ）又は（Ｖ）で表される化合物などがあげられる。 In addition, a known chiral agent can be used in combination with the liquid crystal composition of the present invention. Examples of the chiral agent include compounds represented by the following general formula (IV) or (V).
上記カイラル剤の具体例としては、下記の化合物などがあげられる。 Specific examples of the chiral agent include the following compounds.
また、例えば、特開昭６３−１７５０９５号公報、特開平１−２４２５４２号公報、特開平１−２５８６３５号公報、特開平６−２００２５１号公報、特開２００２−３０８８３３号公報などに提案されているカイラル剤も使用できる。 Further, for example, it has been proposed in JP-A-63-175095, JP-A-1-242542, JP-A-1-258635, JP-A-6-200251, and JP-A-2002-308833. Chiral agents can also be used.
これらのカイラル剤は、単独で使用することもできるが、２種以上を組み合わせて使用することもできる。その場合には、らせんのねじれ方向が異なるものの組み合わせでもねじれ方向が同じものの組み合わせでも良い。また、例えば、特開平７−２５８６４１号公報に提案されているように、コレステリック相の旋回能の温度依存性を正とするものとコレステリック相の旋回能の温度依存性を負とするものとを組みああわせることもできる。
これらカイラル剤の種類及び濃度を変えることでピッチを０．２μ〜３００μの範囲で調整して使用することができる。またこれらのカイラル剤の使用量は、要求されるピッチにより適宜調製される。
These chiral agents can be used alone or in combination of two or more. In that case, a combination of different spiral twisting directions or a combination of the same twisting directions may be used. Further, for example, as proposed in Japanese Patent Application Laid-Open No. 7-258641, the temperature dependence of the turning ability of the cholesteric phase is positive, and the temperature dependence of the turning ability of the cholesteric phase is negative. You can also combine them together.
By changing the kind and concentration of these chiral agents, the pitch can be adjusted within the range of 0.2 to 300 μm. Moreover, the usage-amount of these chiral agents is suitably adjusted with the required pitch.
また、本発明の液晶組成物には、長期に渡って光や熱に対して優れた安定性を付与する目的で、ベンゾトリアゾール系、ベンゾフェノン系、トリアジン系、ベンゾエート系、オキザニリド系、シアノアクリレート系等の紫外線吸収剤；ヒンダードアミン系光安定剤；フェノール系、リン系、硫黄系等の酸化防止剤などを添加することもできる。 The liquid crystal composition of the present invention has a benzotriazole-based, benzophenone-based, triazine-based, benzoate-based, oxanilide-based, cyanoacrylate-based for the purpose of imparting excellent stability to light and heat over a long period of time. UV absorbers such as hindered amine light stabilizers; phenol-based, phosphorus-based, sulfur-based antioxidants, and the like can also be added.
また、本発明の液晶組成物には、帯電防止効果を得るため界面活性剤等を添加することもできる。該化合物としては、例えば、特開昭５９−４６７６号、特開平４−３６３８４号公報、特開平４−１８０９９３号公報、特開平１１−２１２０７０号公報、特開平８−３３７７７９号公報、特開平９−６７５７７号公報、特開２００３−３４２５８０号公報等に提案された化合物などがあげられる。 In addition, a surfactant or the like can be added to the liquid crystal composition of the present invention in order to obtain an antistatic effect. Examples of the compound include JP-A-59-4676, JP-A-4-36384, JP-A-4-180993, JP-A-11-212070, JP-A-8-337779, and JP-A-9. The compounds proposed in JP-A-67577, JP-A-2003-342580 and the like can be mentioned.
本発明の液晶組成物は、液晶セルに封入されて、種々の電気光学表示素子を構成することができる。電気光学表示素子としては、例えば、動的散乱型（ＤＳ）、ゲスト・ホスト型（ＧＨ）、ねじれネマチック型（ＴＮ）、超ねじれネマチック型（ＳＴＮ）、薄膜トランジスター型（ＴＦＴ）、薄膜ダイオード型（ＴＦＤ）、強誘電液晶型（ＦＬＣ）、反強誘電液晶型（ＡＦＬＣ）、高分子分散液晶型（ＰＤ）、垂直配向（ＶＡ）、インプレーンスイッチング（ＩＰＳ）、コレステリックネマチック相転移型などの種種の表示モードが適応され、また、スタティック駆動方式、時分割駆動方式、アクティブマトリックス駆動方式、２周波駆動方式などの種種の駆動方式が適用される。 The liquid crystal composition of the present invention can be sealed in a liquid crystal cell to constitute various electro-optic display elements. Examples of the electro-optic display element include dynamic scattering type (DS), guest-host type (GH), twisted nematic type (TN), super twisted nematic type (STN), thin film transistor type (TFT), and thin film diode type. (TFD), ferroelectric liquid crystal type (FLC), antiferroelectric liquid crystal type (AFLC), polymer dispersed liquid crystal type (PD), vertical alignment (VA), in-plane switching (IPS), cholesteric nematic phase transition type, etc. Various display modes are applied, and various drive methods such as a static drive method, a time-division drive method, an active matrix drive method, and a two-frequency drive method are applied.
本発明の液晶組成物を用いてなる電気光学表示素子は、時計、電卓をはじめ、測定器、自動車用計器、複写機、カメラ、ＯＡ機器、携帯用パソコン、携帯電話などの用途に使用することができる。また、それ以外の用途、例えば、調光窓、光シャッタ、偏光交換素子等にも用いることができるが、特にその特性からカラー携帯電話用途に好適に使用される。 The electro-optic display element using the liquid crystal composition of the present invention is used for applications such as watches, calculators, measuring instruments, automotive instruments, copying machines, cameras, office automation equipment, portable personal computers, mobile phones, etc. Can do. Further, it can be used for other applications such as a dimming window, an optical shutter, a polarization exchange element, etc., but it is preferably used for a color cellular phone due to its characteristics.
以下、実施例をもって本発明を更に詳細に説明する。しかしながら、本発明は以下の実施例によって制限を受けるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the following examples.
＜実施例１＞４−プロピル−３’−フルオロ−４”−（パーフルオロアリルオキシ）−１，１’：４’，１”−ターフェニル〔化合物Ｎｏ．１〕の合成方法 <Example 1> 4-propyl-3'-fluoro-4 "-(perfluoroallyloxy) -1,1 ': 4', 1" -terphenyl [Compound No. 1] 1] synthesis method
フェノール体（１）２６．７ｇ（１１６ミリモル）、トリエチルアミン１２．９１ｇ（１２８ミリモル）、トルエン１３０ｇを仕込み、冷却し、１〜１０℃にコントロールしながら、トリフルオロメタンスルホン酸無水物３４．３６ｇ（１２２ミリモル）を１時間かけて滴下し、１〜１０℃にコントロールしながら１時間反応させた。そこに希塩酸を滴下し、油水分離後、飽和食塩水で３回洗浄し、無水硫酸マグネシウムで乾燥、ろ過、減圧濃縮し、トリフレート体（２）〔茶色液体〕４１．３ｇ（収率９８％）を得た。 Phenol compound (1) 26.7 g (116 mmol), triethylamine 12.91 g (128 mmol), and toluene 130 g were charged, cooled, and controlled at 1 to 10 ° C. while controlling 34.36 g (122 Mmol) was added dropwise over 1 hour, and the mixture was reacted for 1 hour while controlling at 1 to 10 ° C. Dilute hydrochloric acid was added dropwise thereto, and after separation with oil and water, the extract was washed with saturated brine three times, dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure to give 41.3 g of triflate (2) [brown liquid] (yield 98%) )
トリフレート体（２）４１．３１ｇ（１１４ミリモル）、ボロン酸体（３）１９．０６ｇ（１２５ミリモル）、炭酸水素ナトリウム３８．３０ｇ（４５６ミリモル）、リチウムクロライド１４．５０ｇ（３４２ミリモル）、１，４−ジオキサン１１０ｍｌ、水１１０ｍｌを仕込み、窒素気流下、攪拌しながら、Ｐｄ[PPh3]2Cl2錯体０．８００ｇ（１．１４ミリモル）を仕込み、さらに室温にて２０分攪拌し、８０℃に昇温して３時間反応させた。その後冷却して、トルエン１１０ｍｌを仕込み、不溶物をろ過後、油水分離、水洗を３回行った。無水硫酸マグネシウムで乾燥、ろ過後、シリカゲルを仕込み、３０分攪拌、ろ過、減圧濃縮して茶色固体４２．０５ｇを得た。これを酢酸エチル１１０ｇで再結晶し、ターフェニルアニソール体（４）の黄色固体２７．６６ｇ（収率６２％）を得た。 Triflate compound (2) 41.31 g (114 mmol), boronic acid compound (3) 19.06 g (125 mmol), sodium hydrogen carbonate 38.30 g (456 mmol), lithium chloride 14.50 g (342 mmol), 1 , 4-dioxane 110 ml and water 110 ml, while stirring under a nitrogen stream, 0.800 g (1.14 mmol) of Pd [PPh 3 ] 2 Cl 2 complex was added, and the mixture was further stirred at room temperature for 20 minutes. The temperature was raised to 0 ° C. and reacted for 3 hours. Thereafter, the mixture was cooled, 110 ml of toluene was charged, insoluble matters were filtered, and then oil-water separation and water washing were performed three times. After drying over anhydrous magnesium sulfate and filtration, silica gel was charged, stirred for 30 minutes, filtered, and concentrated under reduced pressure to obtain 42.05 g of a brown solid. This was recrystallized from 110 g of ethyl acetate to obtain 27.66 g (yield 62%) of a terphenylanisole (4) yellow solid.
ターフェニルアニソール体（４）２７．６５ｇ（８６．３ミリモル）、ヨウ化水素酸５５質量％水溶液３０．１１ｇ（１２９ミリモル）、酢酸１４０ｇを仕込み、１０５℃で４時間反応させた後、更に１１０℃で３時間反応させた。その後冷却し、水を加え、ろ過し、得られた結晶をさらに水洗した。この結晶にトルエンを添加し、還流脱水後冷却し、フェノール体（５）の淡赤色結晶２４．４ｇ（収率９２％）を得た。 Terphenylanisole (4) 27.65 g (86.3 mmol), hydroiodic acid 55 mass% aqueous solution 30.11 g (129 mmol) and acetic acid 140 g were charged and reacted at 105 ° C. for 4 hours. The reaction was carried out at 0 ° C. for 3 hours. Thereafter, the mixture was cooled, water was added, the mixture was filtered, and the obtained crystals were further washed with water. Toluene was added to the crystals, and after refluxing dehydration, the crystals were cooled to obtain 24.4 g (yield 92%) of pale red crystals of the phenol compound (5).
フェノール体（５）２４．５１ｇ（８０ミリモル）、トリエチルアミン９．７１ｇ（９６ミリモル）、トルエン１０５ｍｌを仕込み、攪拌冷却、４〜１０℃でパーフルオロアリルフルオロサルファイト２１．６ｇ（９２ミリモル）をゆっくり滴下後、同温で１時間反応させた。その後、水を入れ、油水分離、水洗を３回行い、無水硫酸ナトリウムで脱水後、白色固体５２．０４ｇを得た。これをシリカゲルカラム（展開溶媒：ヘキサン）精製し、無色固体を得た。この後、酢酸エチル／メタノール混合溶媒で晶析し、更にヘキサンで晶析し、無色固体２１．５ｇ（収率６２％、純度９９．９％）を得た。 Charge 24.51 g (80 mmol) of phenolic compound (5), 9.71 g (96 mmol) of triethylamine, and 105 ml of toluene, and stir and cool 21.6 g (92 mmol) of perfluoroallylfluorosulfite slowly at 4-10 ° C. After the dropwise addition, the reaction was carried out at the same temperature for 1 hour. Thereafter, water was added, oil-water separation and water washing were performed three times, and after dehydration with anhydrous sodium sulfate, 52.04 g of a white solid was obtained. This was purified on a silica gel column (developing solvent: hexane) to obtain a colorless solid. Thereafter, the mixture was crystallized with a mixed solvent of ethyl acetate / methanol and further crystallized with hexane to obtain 21.5 g (yield 62%, purity 99.9%) of a colorless solid.
得られた化合物は、赤外吸収スペクトル（ＩＲ）及び1Ｈ−ＮＭＲにより目的物であると同定した。分析結果は各々以下の通りである。 The obtained compound was identified as the target product by infrared absorption spectrum (IR) and 1 H-NMR. The analysis results are as follows.
〔ＩＲ〕
２９６３ｃｍ-1、２９３６ｃｍ-1、２８７４ｃｍ-1、１７９４ｃｍ-1、１６２０ｃｍ-1、１５５１ｃｍ-1、１５２４ｃｍ-1、１４８９ｃｍ-1、１４２７ｃｍ-1、１３８９ｃｍ-1、１３１５ｃｍ-1、１２２３ｃｍ-1、１１５３ｃｍ-1、１０９２ｃｍ-1、１０６５ｃｍ-1、１０１１ｃｍ-1、８９５ｃｍ-1、８７６ｃｍ-1、７９１ｃｍ-1、６６７ｃｍ-1、５８６ｃｍ-1、５４４ｃｍ-1、５２１ｃｍ-1、４７５ｃｍ-1、４２２ｃｍ-1、
〔1Ｈ−ＮＭＲ〕
７．７−７．１（ｍ、１１Ｈ）、２．８−２．５（ｔ、２Ｈ）、１．８−１．４（ｍ、２Ｈ），１．１−０．９（ｔ，３Ｈ）
[IR]
2963cm -1, 2936cm -1, 2874cm -1 , 1794cm -1, 1620cm -1, 1551cm -1, 1524cm -1, 1489cm -1, 1427cm -1, 1389cm -1, 1315cm -1, 1223cm -1, 1153cm - 1, 1092cm -1, 1065cm -1, 1011cm -1, 895cm -1, 876cm -1, 791cm -1, 667cm -1, 586cm -1, 544cm -1, 521cm -1, 475cm -1, 422cm -1,
[ 1 H-NMR]
7.7-7.1 (m, 11H), 2.8-2.5 (t, 2H), 1.8-1.4 (m, 2H), 1.1-0.9 (t, 3H) )
相転移温度（℃）は以下の通りであった。
＜実施例２＞１−〔（４’−プロピル−２’，６’−フロオロフェニル）ジフロオロメトキシ〕−３，５−ジフロオロ−４−（パーフルオロアリルオキシ）ベンゼン〔化合物Ｎｏ．２〕の合成方法 Example 2 1-[(4'-propyl-2 ', 6'-fluorophenyl) difluoromethoxy] -3,5-difluoro-4- (perfluoroallyloxy) benzene [Compound No. 2] synthesis method
１，３−ジフルオロ−５−プロピルベンゼン（１）１４．９９ｇ（９６ミリモル）、テトラヒドロフラン７５ｍｌを窒素気流下にて仕込み、−５５℃まで冷却し、ｎ−ブチルリチウム／２．６７モル／Ｌヘキサン溶液３９．５５ｍｌ（１０６ミリモル）を１５分かけて滴下し、１時間反応後、−６２℃まで冷却し、ジフルオロジブロモメタン２４．１７ｇ（１１５ミリモル）をテトラヒドロフラン１０ｍｌに溶解して得られる溶液を１５分かけて滴下し、その後１時間反応させた。室温に戻し、水１５ｍｌを添加し、反応終了とした。反応液にヘキサンおよび水を加え、油水分離し、水洗を３回行った。その後、無水硫酸マグネシウムで脱水後、減圧濃縮し、茶色液体２４．７ｇ得た。これにヘキサン及びシリカゲルを加え、１時間攪拌、ろ過、濃縮し、ＣＦ２Ｂｒ体（２）のオレンジ液体２３．７ｇ（収率５６％）を得た。 1.99 g (96 mmol) of 1,3-difluoro-5-propylbenzene (1) and 75 ml of tetrahydrofuran were charged in a nitrogen stream, cooled to −55 ° C., and n-butyllithium / 2.67 mol / L hexane. 39.55 ml (106 mmol) of the solution was added dropwise over 15 minutes, and after reacting for 1 hour, the solution was cooled to −62 ° C., and 24.17 g (115 mmol) of difluorodibromomethane was dissolved in 10 ml of tetrahydrofuran to obtain a solution of 15 The solution was added dropwise over a period of time, and then reacted for 1 hour. The temperature was returned to room temperature, and 15 ml of water was added to complete the reaction. Hexane and water were added to the reaction solution, oil-water separation was performed, and water washing was performed 3 times. Then, after dehydrating with anhydrous magnesium sulfate, the solution was concentrated under reduced pressure to obtain 24.7 g of a brown liquid. Hexane and silica gel were added thereto, and the mixture was stirred for 1 hour, filtered and concentrated to obtain 23.7 g (yield 56%) of an orange liquid of CF2Br body (2).
フェノール体（３）１４．４５ｇ（６１．２ミリモル）、水酸化ナトリウム３．０１ｇ（９３％、７０ミリモル）、ジメチルイミダゾリジノン７０ｇを仕込み、攪拌しながら６０℃まで昇温し、１時間反応後、ＣＦ２Ｂｒ体（２）２３．７４ｇ（５８．３ミリモル）を５分間かけて滴下し、その後８０℃で２時間反応させた。その後冷却し、希塩酸を滴下し、トルエンを加えて油水分離、水洗を２回行い、飽和食塩水で３回洗浄後、無水硫酸マグネシウムで脱水、ろ過、減圧濃縮し、茶色液体３２ｇを得た。これをシリカゲルカラム（展開溶媒：ヘキサン）精製し、ＣＦ２Ｏ体（４）の黄色液体１８．３５ｇ（純度９６％、収率７１％）を得た。 Phenol compound (3) 14.45 g (61.2 mmol), sodium hydroxide 3.01 g (93%, 70 mmol), and dimethylimidazolidinone 70 g were charged, and the temperature was raised to 60 ° C. with stirring, followed by reaction for 1 hour. Thereafter, 23.74 g (58.3 mmol) of CF2Br body (2) was added dropwise over 5 minutes, and then reacted at 80 ° C. for 2 hours. Thereafter, the mixture was cooled, diluted hydrochloric acid was added dropwise, toluene was added thereto, oil / water separation and water washing were performed twice, washed with saturated saline solution three times, dehydrated with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure to obtain 32 g of a brown liquid. This was purified by a silica gel column (developing solvent: hexane) to obtain 18.35 g (purity 96%, yield 71%) of a yellow liquid of CF2O body (4).
ＣＦ２Ｏ体（４）１８．３５ｇ（４０ミリモル）、Ｐｄ／Ｃ １．８４ｇ（パラジウム５％）、テトラヒドロフラン６０ｍｌを仕込み、窒素置換、室温で５時間反応後、セライトろ過、減圧濃縮後、橙色固体１５．６ｇを得た。これをヘキサンで晶析し、フェノール体（５）の淡黄色結晶１０．９ｇ（収率７８％）を得た。 CF2O body (4) 18.35 g (40 mmol), Pd / C 1.84 g (palladium 5%), and 60 ml of tetrahydrofuran were charged. After nitrogen substitution, reaction at room temperature for 5 hours, Celite filtration, concentration under reduced pressure, orange solid 15 0.6 g was obtained. This was crystallized from hexane to obtain 10.9 g (yield 78%) of pale yellow crystals of the phenol compound (5).
フェノール体（５）１０．８９ｇ（３１．１ミリモル）、トリエチルアミン３．５２ｇ（３７．３ミリモル）、トルエン４５ｍｌを仕込み、攪拌しながら３℃まで冷却し、パーフルオロアリルフルオロサルファイト８．４０ｇ（３５．８ミリモル）を５０分かけて滴下後、同温で１時間反応させた。その後、水を入れ、油水分離後、水洗を３回行い、無水硫酸ナトリウムで脱水後、黄色液体１４．５３ｇを得た。これをシリカゲルカラム（展開溶媒：ヘキサン）精製し、無色液体１１．７３ｇを得た。この後、メタノールで晶析、蒸留、更にメタノール晶析し、無色液体９．１ｇ（収率６１％、純度９９．９％） 10.89 g (31.1 mmol) of the phenol compound (5), 3.52 g (37.3 mmol) of triethylamine and 45 ml of toluene were charged, and the mixture was cooled to 3 ° C. with stirring, and 8.40 g of perfluoroallylfluorosulfite ( 35.8 mmol) was added dropwise over 50 minutes, followed by reaction at the same temperature for 1 hour. Thereafter, water was added, oil-water separation was performed, and water washing was performed three times. After dehydration with anhydrous sodium sulfate, 14.53 g of a yellow liquid was obtained. This was purified on a silica gel column (developing solvent: hexane) to obtain 11.73 g of a colorless liquid. After that, crystallization with methanol, distillation, and further crystallization with methanol gave 9.1 g of colorless liquid (yield 61%, purity 99.9%).
得られた化合物は、赤外吸収スペクトル（ＩＲ）及び1Ｈ−ＮＭＲにより目的物であると同定した。分析結果は各々以下の通りである。 The obtained compound was identified as the target product by infrared absorption spectrum (IR) and 1 H-NMR. The analysis results are as follows.
〔ＩＲ〕
３１０５ｃｍ-1、２９６６ｃｍ-1、２９３９ｃｍ-1、２８７８ｃｍ-1、１７９０ｃｍ-1、１６４３ｃｍ-1、１６１２ｃｍ-1、１５８２ｃｍ-1、１５０８ｃｍ-1、１４４７ｃｍ-1、１３８５ｃｍ-1、１３１９ｃｍ-1、１２９６ｃｍ-1、１２２７ｃｍ-1、１２０４ｃｍ-1、１１５０ｃｍ-1、１１１１ｃｍ-1、１０１８ｃｍ-1、８７２ｃｍ-1、８４５ｃｍ-1、７９９ｃｍ-1、７４８ｃｍ-1、７１４ｃｍ-1、６９１ｃｍ-1、６６４ｃｍ-1、６２９ｃｍ-1、５６３ｃｍ-1、５２１ｃｍ-1、
〔1Ｈ−ＮＭＲ〕
７．０−６．６（ｍ、４Ｈ）、２．８−２．５（ｔ、２Ｈ）、１．８−１．４（ｍ、２Ｈ），１．１−０．９（ｔ，３Ｈ）
[IR]
3105 cm −1 , 2966 cm −1 , 2939 cm −1 , 2878 cm −1 , 1790 cm −1 , 1643 cm −1 , 1612 cm −1 , 1582 cm −1 , 1508 cm −1 , 1447 cm −1 , 1385 cm −1 , 1319 cm −1 , 1296 cm − 1, 1227cm -1, 1204cm -1, 1150cm -1, 1111cm -1, 1018cm -1, 872cm -1, 845cm -1, 799cm -1, 748cm -1, 714cm -1, 691cm -1, 664cm -1, 629 cm −1 , 563 cm −1 , 521 cm −1 ,
[ 1 H-NMR]
7.0-6.6 (m, 4H), 2.8-2.5 (t, 2H), 1.8-1.4 (m, 2H), 1.1-0.9 (t, 3H) )
＜実施例３＞４−プロピル−３，５，３’−トリフルオロ−４”−（パーフルオロアリルオキシ）−１，１’：４’，１”−ターフェニル〔化合物Ｎｏ．３〕の合成方法 Example 3 4-Propyl-3,5,3'-trifluoro-4 "-(perfluoroallyloxy) -1,1 ': 4', 1" -terphenyl [Compound No. 3] 3] synthesis method
窒素気流下、トリフレート体（１）５．５ｇ（１５．２ミリモル）、ボロン酸体（２）３．１３ｇ（１６．７ミリモル）、炭酸水素ナトリウム５．０９ｇ（６０．６ミリモル）、Ｐｄ[PPh3]2Cl2錯体０．１０６ｇ（０．１５１ミリモル）リチウムクロライド１．９３ｇ（４５．５ミリモル）、１，４−ジオキサン１６ｇ、水１６ｇを仕込み、８０℃に昇温して５．５時間反応させた。その後室温まで冷却して、希塩酸及び酢酸エチルを加え、油水分離した。飽和食塩水で５回洗浄し、硫酸マグネシウムで乾燥、脱溶媒し、黒白色粉末５．７ｇを得た。シリカゲルカラム（展開溶媒：ヘキサン／酢酸エチル）精製し、ターフェニルアニソール体（３）の白色粉末５．０ｇ（収率９１．９％）を得た。 Under a nitrogen stream, 5.5 g (15.2 mmol) of the triflate (1), 3.13 g (16.7 mmol) of the boronic acid (2), 5.09 g (60.6 mmol) of sodium hydrogen carbonate, Pd [PPh 3 ] 2 Cl 2 complex 0.106 g (0.151 mmol) lithium chloride 1.93 g (45.5 mmol), 1,4-dioxane 16 g and water 16 g were charged, and the temperature was raised to 80 ° C. The reaction was allowed for 5 hours. Thereafter, the mixture was cooled to room temperature, diluted hydrochloric acid and ethyl acetate were added, and oil and water were separated. The extract was washed 5 times with saturated brine, dried over magnesium sulfate and desolvated to obtain 5.7 g of a black white powder. Purification by a silica gel column (developing solvent: hexane / ethyl acetate) gave 5.0 g (yield 91.9%) of a white powder of terphenylanisole (3).
窒素気流下、ターフェニルアニソール体（３）５．０ｇ（１３．９ミリモル）、ヨウ化水素酸５２質量％水溶液７．２ｇ（２９．１ミリモル）、酢酸２３．９ｇを仕込み、攪拌しながら、１０５℃で４時間反応させた。その後冷却し、トルエン、酢酸エチルおよび水を加え、油水分離した。チオ硫酸ナトリウム水溶液で洗浄し、飽和食塩水で洗浄し、無水硫酸マグネシウムで乾燥、脱溶媒を行い、黄白色粉末４．８ｇを得た。精製は、シリカゲルカラム（展開溶媒：ヘキサン／酢酸エチル）にて行い、フェノール体（４）の白色粉末４．３ｇ（収率８９．９％）を得た。 Under a nitrogen stream, 5.0 g (13.9 mmol) of terphenylanisole (3), 7.2 g (29.1 mmol) of 52% by weight aqueous hydroiodic acid, and 23.9 g of acetic acid were charged and stirred. The reaction was carried out at 105 ° C. for 4 hours. Thereafter, the mixture was cooled, and toluene, ethyl acetate and water were added to separate the oil and water. The extract was washed with an aqueous sodium thiosulfate solution, washed with saturated brine, dried over anhydrous magnesium sulfate, and desolventized to obtain 4.8 g of a yellowish white powder. Purification was carried out using a silica gel column (developing solvent: hexane / ethyl acetate) to obtain 4.3 g (yield 89.9%) of a white powder of the phenol compound (4).
窒素気流下、フェノール体（４）４．３ｇ（１２．５ミリモル）、トリエチルアミン１．５８ｇ（１５．６ミリモル）、トルエン１３ｇを仕込み、攪拌冷却、１５℃以下でパーフルオロアリルフルオロサルファイト３．２３ｇ（１３．８ミリモル）をゆっくり滴下後、５℃で１時間反応させた。その後、水および酢酸エチルを加えて油水分離した。希塩酸を加えて分液後、飽和食塩水で３回洗浄し、無水硫酸マグネシウム乾燥、脱溶媒を行い、黄白色粉末５．８ｇを得た。シリカゲルカラム（展開溶媒：ヘキサン／トルエン）精製し、エタノールによる晶析２回行い、白色結晶４．５ｇ（収率７５．８％、純度１００％）を得た。 Under a nitrogen stream, 4.3 g (12.5 mmol) of the phenol compound (4), 1.58 g (15.6 mmol) of triethylamine and 13 g of toluene were charged, stirred and cooled, and perfluoroallylfluorosulfite 3. 23 g (13.8 mmol) was slowly added dropwise, followed by reaction at 5 ° C. for 1 hour. Then, water and ethyl acetate were added and oil-water separation was carried out. Dilute hydrochloric acid was added for liquid separation, followed by washing with saturated brine three times, drying over anhydrous magnesium sulfate and desolvation to obtain 5.8 g of a yellowish white powder. The silica gel column (developing solvent: hexane / toluene) was purified and crystallized twice with ethanol to obtain 4.5 g of white crystals (yield 75.8%, purity 100%).
得られた化合物は、赤外吸収スペクトル（ＩＲ）及び1Ｈ−ＮＭＲにより目的物であると同定した。分析結果は各々以下の通りである。 The obtained compound was identified as the target product by infrared absorption spectrum (IR) and 1 H-NMR. The analysis results are as follows.
〔ＩＲ〕
３４４４ｃｍ-1、２９６６ｃｍ-1、２９３６ｃｍ-1、２８７８ｃｍ-1、１９１３ｃｍ-1、１７９４ｃｍ-1、１６２４ｃｍ-1、１６０５ｃｍ-1、１４９３ｃｍ-1、１３８９ｃｍ-1、１３２３ｃｍ-1、１２３１ｃｍ-1、１２０７ｃｍ-1、１０１８ｃｍ-1、８２１ｃｍ-1、７９９ｃｍ-1、
〔1Ｈ−ＮＭＲ〕
７．７−７．１（ｍ、９Ｈ）、２．８−２．５（ｔ、２Ｈ）、１．９−１．４（ｍ、２Ｈ），１．１−０．８（ｔ，３Ｈ）
[IR]
3444cm -1, 2966cm -1, 2936cm -1 , 2878cm -1, 1913cm -1, 1794cm -1, 1624cm -1, 1605cm -1, 1493cm -1, 1389cm -1, 1323cm -1, 1231cm -1, 1207cm - 1, 1018cm -1, 821cm -1, 799cm -1,
[ 1 H-NMR]
7.7-7.1 (m, 9H), 2.8-2.5 (t, 2H), 1.9-1.4 (m, 2H), 1.1-0.8 (t, 3H) )
相転移温度（℃）は以下の通りであった。
＜実施例４＞４−プロピル−３，５−ジフルオロ−３’−クロロ−４”−（パーフルオロアリルオキシ）−１，１’：４’，１”−ターフェニル〔化合物Ｎｏ．４〕の合成方法 Example 4 4-propyl-3,5-difluoro-3'-chloro-4 "-(perfluoroallyloxy) -1,1 ': 4', 1" -terphenyl [Compound No. 4] 4] synthesis method
窒素気流下、トリフレート体（１）１１．６ｇ（２９．２ミリモル）、ボロン酸体（２）６．３ｇ（３３．７ミリモル）、炭酸水素ナトリウム１０．３ｇ（１２３ミリモル）、Ｐｄ[PPh3]2Cl2錯体０．４３０ｇ（０．６１２ミリモル）、リチウムクロライド３．８９ｇ（９１．８ミリモル）、１，４−ジオキサン３３ｍｌ、水３３ｍｌを仕込み、８０℃に昇温して６．５時間反応させた。その後冷却して、トルエンを加えて油水分離した。水洗して硫酸マグネシウムで乾燥、脱溶媒し、黒色液体１２．０ｇを得た。シリカゲルカラム（展開溶媒：ヘキサン／酢酸エチル）精製し、ターフェニルアニソール体（３）の黄色透明液体１０．５ｇ（収率９２．２％）を得た。 Under a nitrogen stream, 11.6 g (29.2 mmol) of the triflate (1), 6.3 g (33.7 mmol) of the boronic acid (2), 10.3 g (123 mmol) of sodium bicarbonate, Pd [PPh 3 ] 2 Cl 2 complex 0.430 g (0.612 mmol), lithium chloride 3.89 g (91.8 mmol), 1,4-dioxane 33 ml, water 33 ml were charged, and the temperature was raised to 80 ° C. to 6.5. Reacted for hours. After cooling, toluene was added to separate the oil and water. It was washed with water, dried over magnesium sulfate and desolvated to obtain 12.0 g of a black liquid. Purification by silica gel column (developing solvent: hexane / ethyl acetate) gave 10.5 g (yield 92.2%) of a terphenylanisole (3) as a yellow transparent liquid.
窒素気流下、ターフェニルアニソール体（３）１０．５ｇ（２７．０ミリモル）、ヨウ化水素酸５２質量％水溶液８．６ｇ（６７．５ミリモル）、酢酸４８．５ｇを仕込み、攪拌しながら、１０５℃で９時間反応させた。その後、酢酸エチルおよび水を加え油水分離した。チオ硫酸ナトリウム水溶液で洗浄し、水洗後、無水硫酸マグネシウムで乾燥、脱溶媒を行い、黄白色粉末１０．６ｇを得た。シリカゲルカラム（展開溶媒：ヘキサン／酢酸エチル）精製し、フェノール体（４）の白色粉末９．６ｇ（収率９８％）を得た。 Under a nitrogen stream, 10.5 g (27.0 mmol) of terphenylanisole (3), 8.6 g (67.5 mmol) of 52% by weight aqueous solution of hydroiodic acid, and 48.5 g of acetic acid were charged and stirred. The reaction was carried out at 105 ° C. for 9 hours. Then, ethyl acetate and water were added and oil-water separation was carried out. It was washed with an aqueous sodium thiosulfate solution, washed with water, dried over anhydrous magnesium sulfate, and desolvated to obtain 10.6 g of a yellowish white powder. Purification by silica gel column (developing solvent: hexane / ethyl acetate) gave 9.6 g (yield 98%) of a white powder of phenol (4).
窒素気流下、フェノール体（４）９．４ｇ（２６．０ミリモル）、トリエチルアミン３．２９ｇ（３２．５ミリモル）、トルエン２８ｍｌを仕込み、攪拌冷却、５℃以下でパーフルオロアリルフルオロサルファイト６．９ｇ（２８．６ミリモル）をゆっくり滴下後、５℃で３０分反応させた。その後、１０％塩酸水溶液を加え分液後、水洗し、無水硫酸マグネシウム乾燥、脱溶媒を行い、白色粉末１１．６ｇを得た。シリカゲルカラム（ヘキサン／トルエン）精製し、メタノール／エタノールによる晶析２回行い、白色結晶８．６ｇ（収率６７．３％、純度９９．８％）を得た Under a nitrogen stream, 9.4 g (26.0 mmol) of the phenol compound (4), 3.29 g (32.5 mmol) of triethylamine, and 28 ml of toluene were charged, stirred, cooled, and perfluoroallylfluorosulfite at 5.degree. 9 g (28.6 mmol) was slowly added dropwise, followed by reaction at 5 ° C. for 30 minutes. Thereafter, a 10% aqueous hydrochloric acid solution was added for liquid separation, followed by washing with water, drying over anhydrous magnesium sulfate, and removal of the solvent to obtain 11.6 g of a white powder. Purification by silica gel column (hexane / toluene) and crystallization with methanol / ethanol were performed twice to obtain 8.6 g of white crystals (yield 67.3%, purity 99.8%).
得られた化合物は、赤外吸収スペクトル（ＩＲ）及び1Ｈ−ＮＭＲにより目的物であると同定した。分析結果は各々以下の通りである。 The obtained compound was identified as the target product by infrared absorption spectrum (IR) and 1 H-NMR. The analysis results are as follows.
〔ＩＲ〕
３４９９ｃｍ-1、２９６３ｃｍ-1、２９３６ｃｍ-1、２８７４ｃｍ-1、１９１３ｃｍ-1、１７９４ｃｍ-1、１６２８ｃｍ-1、１６０１ｃｍ-1、１４８１ｃｍ-1、１４３５ｃｍ-1、１３８５ｃｍ-1、１３１９ｃｍ-1、１２３１ｃｍ-1、１２０４ｃｍ-1、１０１８ｃｍ-1、８１８ｃｍ-1、
〔1Ｈ−ＮＭＲ〕
７．８−７．０（ｍ、９Ｈ）、２．７−２．５（ｔ、２Ｈ）、１．９−１．４（ｍ、２Ｈ），１．１−０．８（ｔ，３Ｈ）
[IR]
3499 cm −1 , 2963 cm −1 , 2936 cm −1 , 2874 cm −1 , 1913 cm −1 , 1794 cm −1 , 1628 cm −1 , 1601 cm −1 , 1481 cm −1 , 1435 cm −1 , 1385 cm −1 , 1319 cm −1 , 1231 cm − 1, 1204cm -1, 1018cm -1, 818cm -1,
[ 1 H-NMR]
7.8-7.0 (m, 9H), 2.7-2.5 (t, 2H), 1.9-1.4 (m, 2H), 1.1-0.8 (t, 3H) )
相転移温度（℃）は以下の通りであった。
＜実施例５＞４−プロピル−２，３’，５’−トリフルオロ−４’−〔[４”−（パーフルオロアリルオキシ）−３，５−ジフルオロフェノキシ]ジフルオロメチル−１，１’−ビフェニル〔化合物Ｎｏ．５〕の合成方法 Example 5 4-propyl-2,3 ′, 5′-trifluoro-4 ′-[[4 ”-(perfluoroallyloxy) -3,5-difluorophenoxy] difluoromethyl-1,1′- Method for synthesizing biphenyl [Compound No. 5]
窒素雰囲気下、ビフェニル体（１）１３．３ｇ（４９．９ミリモル）、テトラヒドロフラン６７ｍｌを仕込み、−６０℃まで冷却し、ｎ−ブチルリチウム／２．６７モル／Ｌヘキサン溶液２０．９ｍｌ（５５．８ミリモル）を１５分かけて滴下し、１時間反応後、−６０℃以下でジフルオロジブロモメタン１３．４ｇ（６３．６ミリモル）を滴下し、その後２時間反応させた。０℃まで昇温し、ヘキサンおよび水を添加し、攪拌分液した。飽和食塩水洗浄で中性を確認後、無水硫酸マグネシウムで乾燥、脱溶剤を行い、茶色液体１９．４ｇ（収率８１．１％）を得た。 Under a nitrogen atmosphere, 13.3 g (49.9 mmol) of the biphenyl compound (1) and 67 ml of tetrahydrofuran were charged, cooled to −60 ° C., and 20.9 ml (55.55 ml) of n-butyllithium / 2.67 mol / L hexane solution. 8 mmol) was added dropwise over 15 minutes, and after 1 hour of reaction, 13.4 g (63.6 mmol) of difluorodibromomethane was added dropwise at −60 ° C. or lower, followed by reaction for 2 hours. The temperature was raised to 0 ° C., hexane and water were added, and the mixture was stirred and separated. After neutrality was confirmed by washing with a saturated saline solution, drying and solvent removal were performed with anhydrous magnesium sulfate to obtain 19.4 g (yield 81.1%) of a brown liquid.
フェノール体（３）６．０ｇ（２５．０ミリモル）、水酸化ナトリウム１．１７ｇ（２７．２ミリモル）、ジメチルイミダゾリジノン３０ｇを仕込み、攪拌しながら６０℃まで昇温し、１．５時間反応後、ＣＦ２Ｂｒ体（２）１０．０ｇ（２０．９ミリモル）を滴下し、８０℃で８．５時間反応させた。その後冷却し、トルエンおよび水を加え攪拌分液し、５％塩酸で洗浄、飽和食塩水洗浄で中和確認後、無水硫酸マグネシウムで脱水、脱溶媒行い、黄白色固体１４．２ｇを得た。エタノール晶析を行い、ＣＦ２Ｏ体（４）の白色粉末６．２ｇ（収率５５．１％）を得た。 Phenol compound (3) (6.0 g, 25.0 mmol), sodium hydroxide (1.17 g, 27.2 mmol) and dimethylimidazolidinone (30 g) were charged, and the temperature was raised to 60 ° C. with stirring for 1.5 hours. After the reaction, 10.0 g (20.9 mmol) of CF2Br body (2) was added dropwise and reacted at 80 ° C. for 8.5 hours. After cooling, toluene and water were added, and the mixture was stirred and separated, washed with 5% hydrochloric acid and neutralized with saturated brine, dehydrated with anhydrous magnesium sulfate, and desolvated to give 14.2 g of a yellowish white solid. Crystallization with ethanol gave 6.2 g (yield 55.1%) of white powder of CF2O body (4).
ＣＦ２Ｏ体（４）６．１ｇ（１１．４ミリモル）、Ｐｄ／Ｃ ０．５１ｇ（パラジウム５％）、テトラヒドロフラン１２．６ｇを仕込み、水素置換、室温で４．５時間反応後、セライトろ過、減圧濃縮後、茶白色固体５．２ｇを得た。これをシリカゲル（展開溶媒：ヘキサン／酢酸エチル）精製し、フェノール体（５）の白色粉末４．８ｇ（収率９４．９％、）を得た。 CF2O body (4) 6.1 g (11.4 mmol), Pd / C 0.51 g (palladium 5%) and tetrahydrofuran 12.6 g were charged, hydrogen exchanged, reacted at room temperature for 4.5 hours, celite filtration, reduced pressure After concentration, 5.2 g of a brownish white solid was obtained. This was purified by silica gel (developing solvent: hexane / ethyl acetate) to obtain 4.8 g (yield 94.9%) of a white powder of the phenol compound (5).
窒素気流下、フェノール体（５）４．８ｇ（１０．８ミリモル）、トリエチルアミン１．３１ｇ（１２．９ミリモル）、トルエン１４ｇを仕込み、攪拌しながら−２０℃まで冷却し、パーフルオロアリルフルオロサルファイト２．９ｇ（１１．９ミリモル）をゆっくり滴下後、０℃以下で１時間反応させた。その後、水を入れ、油水分離を行った。５％塩酸を加え分液後、水洗し、無水硫酸マグネシウムで乾燥、脱溶媒を行い、黄白色粉末を得た。シリカゲルカラム（展開溶媒：ヘキサン／トルエン）精製し、エタノール晶析を行い、白色粉末４．６ｇ（収率７８．９％、純度９９．９％）を得た。 Under a nitrogen stream, 4.8 g (10.8 mmol) of phenol (5), 1.31 g (12.9 mmol) of triethylamine and 14 g of toluene were charged, and the mixture was cooled to −20 ° C. with stirring, and perfluoroallylfluorosal. After slowly dropping 2.9 g (11.9 mmol) of phyto, the mixture was reacted at 0 ° C. or less for 1 hour. Then, water was added and oil-water separation was performed. 5% Hydrochloric acid was added, and the mixture was separated, washed with water, dried over anhydrous magnesium sulfate and desolvated to give a yellowish white powder. The silica gel column (developing solvent: hexane / toluene) was purified, and ethanol crystallization was performed to obtain 4.6 g (yield 78.9%, purity 99.9%) of white powder.
得られた化合物は、赤外吸収スペクトル（ＩＲ）及び1Ｈ−ＮＭＲにより目的物であると同定した。分析結果は各々以下の通りである。 The obtained compound was identified as the target product by infrared absorption spectrum (IR) and 1 H-NMR. The analysis results are as follows.
〔ＩＲ〕
３４３７ｃｍ-1、３１０１ｃｍ-1、２９７０ｃｍ-1、２９３９ｃｍ-1、２８７８ｃｍ-1、１７９０ｃｍ-1、１６３９ｃｍ-1、１５８２ｃｍ-1、１５０４ｃｍ-1、１４５４ｃｍ-1、１４０７ｃｍ-1、１３８５ｃｍ-1、１３４６ｃｍ-1、１３０４ｃｍ-1、１２２３ｃｍ-1、１１６９ｃｍ-1、１１１９ｃｍ-1、１０８４ｃｍ-1、１０３８ｃｍ-1、１０１４ｃｍ-1、
〔1Ｈ−ＮＭＲ〕
７．５−６．９（ｍ、７Ｈ）、２．７−２．２（ｔ、２Ｈ）、１．９−１．２（ｍ、２Ｈ），１．１−０．８（ｔ，３Ｈ）
[IR]
3437cm -1, 3101cm -1, 2970cm -1 , 2939cm -1, 2878cm -1, 1790cm -1, 1639cm -1, 1582cm -1, 1504cm -1, 1454cm -1, 1407cm -1, 1385cm -1, 1346cm - 1 , 1304 cm −1 , 1223 cm −1 , 1169 cm −1 , 1119 cm −1 , 1084 cm −1 , 1038 cm −1 , 1014 cm −1 ,
[ 1 H-NMR]
7.5-6.9 (m, 7H), 2.7-2.2 (t, 2H), 1.9-1.2 (m, 2H), 1.1-0.8 (t, 3H) )
相転移温度（℃）は以下の通りであった。
＜実施例６＞４−プロピル−３’，５’−ジフルオロ−４’−〔[４”−（パーフルオロアリルオキシ）−３，５−ジフルオロフェノキシ]ジフルオロメチル−１，１’−ビフェニル〔化合物Ｎｏ．６〕の合成方法 <Example 6> 4-propyl-3 ', 5'-difluoro-4'-[[4 "-(perfluoroallyloxy) -3,5-difluorophenoxy] difluoromethyl-1,1'-biphenyl [compound No. 6] synthesis method
窒素雰囲気下、フェノール体（１）２１．５ｇ（５６．５ミリモル）、トリエチルアミン６．１ｇ（６０．５４ミリモル）、トルエン１１２ｇを仕込み、攪拌しながら５℃まで冷却し、パーフルオロアリルフルオロサルファイト１２．８ｇ（５５．５ミリモル）をゆっくり滴下後、５℃以下で１時間反応させた後、水洗処理を行った。シリカゲルカラム（展開溶媒ヘキサン）精製し、エタノール晶析を行い、白色粉末１６．４ｇ（収率５９％、純度９９．９％）を得た。 Under a nitrogen atmosphere, 21.5 g (56.5 mmol) of phenolic compound (1), 6.1 g (60.54 mmol) of triethylamine and 112 g of toluene were charged and cooled to 5 ° C. with stirring, and perfluoroallylfluorosulfite. After 12.8 g (55.5 mmol) was slowly added dropwise, the mixture was reacted at 5 ° C. or lower for 1 hour, and then washed with water. Purification by silica gel column (developing solvent hexane) and crystallization of ethanol were performed to obtain 16.4 g of white powder (yield 59%, purity 99.9%).
得られた化合物は、赤外吸収スペクトル（ＩＲ）及び1Ｈ−ＮＭＲにより目的物であると同定した。分析結果は各々以下の通りである。 The obtained compound was identified as the target product by infrared absorption spectrum (IR) and 1 H-NMR. The analysis results are as follows.
〔ＩＲ〕
３４４０ｃｍ-1、３０８６ｃｍ-1、２９７４ｃｍ-1、２９３９ｃｍ-1、２８８２ｃｍ-1、１９１７ｃｍ-1、１７９４ｃｍ-1、１６４３ｃｍ-1、１６１２ｃｍ-1、１５６２ｃｍ-1、１５８５ｃｍ-1、１５０４ｃｍ-1、１４３９ｃｍ-1、１３９３ｃｍ-1、１３０４ｃｍ-1、１２１９ｃｍ-1、１１９６ｃｍ-1、１１３４ｃｍ-1、１０２６ｃｍ-1、８７７ｃｍ-1、８３３ｃｍ-1、７９９ｃｍ-1、７４５ｃｍ-1、
〔1Ｈ−ＮＭＲ〕
７．６−６．８（ｍ、８Ｈ）、２．８−２．５（ｔ、２Ｈ）、１．９−１．４（ｍ、２Ｈ），１．１−０．７（ｔ，３Ｈ）
[IR]
3440 cm −1 , 3086 cm −1 , 2974 cm −1 , 2939 cm −1 , 2882 cm −1 , 1917 cm −1 , 1794 cm −1 , 1643 cm −1 , 1612 cm −1 , 1562 cm −1 , 1585 cm −1 , 1504 cm −1 , 1439 cm − 1 , 1393 cm −1 , 1304 cm −1 , 1219 cm −1 , 1196 cm −1 , 1134 cm −1 , 1026 cm −1 , 877 cm −1 , 833 cm −1 , 799 cm −1 , 745 cm −1 ,
[ 1 H-NMR]
7.6-6.8 (m, 8H), 2.8-2.5 (t, 2H), 1.9-1.4 (m, 2H), 1.1-0.7 (t, 3H) )
相転移温度（℃）は以下の通りであった。
＜比較例１＞
下記の比較化合物１の相転移温度を示した。類似構造を有する本願発明の化合物Ｎｏ．６と異なり、液晶相を示さない。
<Comparative Example 1>
The phase transition temperature of the following comparative compound 1 was shown. Compound No. 1 of the present invention having a similar structure. Unlike 6, it does not show a liquid crystal phase.
＜比較例２＞
下記の比較化合物２の相転移温度を示した。類似構造を有する本願発明の化合物Ｎｏ．３と異なり、冷却時にのみ液晶相を発現するモノトロピックな液晶化合物である。
<Comparative example 2>
The phase transition temperature of the following comparative compound 2 was shown. Compound No. 1 of the present invention having a similar structure. 3 is a monotropic liquid crystal compound that develops a liquid crystal phase only when cooled.
＜実施例７及び比較例３＞
下記に示した母液晶に対し、本願発明の化合物及び比較化合物を１０質量％含有して液晶組成物を調整し、ＮＴ点、光学異方性（Δｎ）及び誘電率異方性（Δε）を測定した。その結果を〔表１〕に示した。
<Example 7 and Comparative Example 3>
With respect to the mother liquid crystal shown below, the liquid crystal composition was prepared by containing 10% by mass of the compound of the present invention and the comparative compound, and the NT point, optical anisotropy (Δn) and dielectric anisotropy (Δε) were determined. It was measured. The results are shown in [Table 1].
実施例から明らかなように、本願発明の含ハロゲン化合物は、ネマチック液晶組成物に含有させることで、上限温度をほとんど下げることなく、高いΔｎと高いΔεを提供しうる材料であり、本発明の含ハロゲン化合物を含有して得られる液晶組成物は、あらゆる表示方式およびあらゆる駆動方式の電気光学素子用の液晶材料として有用なものである。 As is apparent from the examples, the halogen-containing compound of the present invention is a material that can provide a high Δn and a high Δε without substantially lowering the maximum temperature by being contained in the nematic liquid crystal composition. A liquid crystal composition obtained by containing a halogen-containing compound is useful as a liquid crystal material for electro-optic elements of all display systems and all drive systems.
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