JP5382406B2 - 1- (Trifluoromethoxy) naphthalene derivative - Google Patents
1- (Trifluoromethoxy) naphthalene derivative Download PDFInfo
- Publication number
- JP5382406B2 JP5382406B2 JP2008180081A JP2008180081A JP5382406B2 JP 5382406 B2 JP5382406 B2 JP 5382406B2 JP 2008180081 A JP2008180081 A JP 2008180081A JP 2008180081 A JP2008180081 A JP 2008180081A JP 5382406 B2 JP5382406 B2 JP 5382406B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- carbon atoms
- independently
- liquid crystal
- general formula
- 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.)
- Expired - Fee Related
Links
- REEVHKPBTDJGPJ-UHFFFAOYSA-N 1-(trifluoromethoxy)naphthalene Chemical class C1=CC=C2C(OC(F)(F)F)=CC=CC2=C1 REEVHKPBTDJGPJ-UHFFFAOYSA-N 0.000 title claims 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 63
- 150000001875 compounds Chemical class 0.000 claims description 63
- 239000004973 liquid crystal related substance Substances 0.000 claims description 59
- 239000000203 mixture Substances 0.000 claims description 47
- 125000000217 alkyl group Chemical group 0.000 claims description 32
- 125000001153 fluoro group Chemical group F* 0.000 claims description 19
- 125000003545 alkoxy group Chemical group 0.000 claims description 15
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 229910052731 fluorine Inorganic materials 0.000 claims description 13
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims description 11
- -1 pyridine-2,5-diyl group Chemical group 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000003302 alkenyloxy group Chemical group 0.000 claims description 9
- 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 claims description 9
- 239000000470 constituent Substances 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000012044 organic layer Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 150000004782 1-naphthols Chemical class 0.000 description 7
- ONBSGHCEEBKPIY-IYARVYRRSA-N C(CCC)OC1=CC=C2C=C(C(=C(C2=C1OC(F)(F)F)F)F)CC[C@@H]1CC[C@H](CC1)CCC Chemical compound C(CCC)OC1=CC=C2C=C(C(=C(C2=C1OC(F)(F)F)F)F)CC[C@@H]1CC[C@H](CC1)CCC ONBSGHCEEBKPIY-IYARVYRRSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 0 [*-]c1ccc(cc(CCC(CC2)=CCCC2N)c(F)c2F)c2c1[*+2] Chemical compound [*-]c1ccc(cc(CCC(CC2)=CCCC2N)c(F)c2F)c2c1[*+2] 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- JIUQNSNBMPHUIR-UHFFFAOYSA-N 1-(trichloromethoxy)naphthalene Chemical class C1=CC=C2C(OC(Cl)(Cl)Cl)=CC=CC2=C1 JIUQNSNBMPHUIR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 4
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZVJOCJICMXJUOX-IYARVYRRSA-N CCCCOC(C=CC(C1=C2F)=CC([C@H]3CC[C@H](CCC)CC3)=C2F)=C1OCC=O Chemical compound CCCCOC(C=CC(C1=C2F)=CC([C@H]3CC[C@H](CCC)CC3)=C2F)=C1OCC=O ZVJOCJICMXJUOX-IYARVYRRSA-N 0.000 description 3
- WGTQYOLKAOVJCT-IYARVYRRSA-N CCCCOCCC(C=CC(C1=C2F)=CC([C@H]3CC[C@H](CCC)CC3)=C2F)=C1O Chemical compound CCCCOCCC(C=CC(C1=C2F)=CC([C@H]3CC[C@H](CCC)CC3)=C2F)=C1O WGTQYOLKAOVJCT-IYARVYRRSA-N 0.000 description 3
- PYAIDWRBPVZPJZ-HDJSIYSDSA-N CCC[C@H](CC1)CC[C@@H]1C(C=C(C=CC(O)=C1OCC=O)C1=C1F)=C1F Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C(C=CC(O)=C1OCC=O)C1=C1F)=C1F PYAIDWRBPVZPJZ-HDJSIYSDSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 239000012769 display material Substances 0.000 description 3
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical class CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- DSLKOTQBUFGMQY-UHFFFAOYSA-N 1,2,3-trifluoronaphthalene Chemical class C1=CC=C2C(F)=C(F)C(F)=CC2=C1 DSLKOTQBUFGMQY-UHFFFAOYSA-N 0.000 description 2
- APBRTNCOFUFMAA-UHFFFAOYSA-N 1-ethylnaphthalen-2-ol Chemical compound C1=CC=C2C(CC)=C(O)C=CC2=C1 APBRTNCOFUFMAA-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 2
- JOSUGFWMXAVXSM-WKILWMFISA-N CCCCOC(C(OC)=CC(C1=C2F)=CC([C@H]3CC[C@H](CCC)CC3)=C2F)=C1O Chemical compound CCCCOC(C(OC)=CC(C1=C2F)=CC([C@H]3CC[C@H](CCC)CC3)=C2F)=C1O JOSUGFWMXAVXSM-WKILWMFISA-N 0.000 description 2
- UAVWHLLYSNOJKL-PTEGZUARSA-N CCCCOCC(C=O)C(C1=C2F)=CC=CC1=CC([C@H]1CC[C@H](CCC)CC1)=C2F Chemical compound CCCCOCC(C=O)C(C1=C2F)=CC=CC1=CC([C@H]1CC[C@H](CCC)CC1)=C2F UAVWHLLYSNOJKL-PTEGZUARSA-N 0.000 description 2
- GCXOHMSYMXPEND-NJIVVBIYSA-N CCC[C@H](CC1)CC[C@@H]1C(C=C(C=CC(O)=C1C(C)C=O)C1=C1F)=C1F Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C(C=CC(O)=C1C(C)C=O)C1=C1F)=C1F GCXOHMSYMXPEND-NJIVVBIYSA-N 0.000 description 2
- XUWSDBGXLHAXJU-HDJSIYSDSA-N CCC[C@H](CC1)CC[C@@H]1C(C=C(C=CC(O)=C1CC)C1=C1F)=C1F Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C(C=CC(O)=C1CC)C1=C1F)=C1F XUWSDBGXLHAXJU-HDJSIYSDSA-N 0.000 description 2
- UPKSKMGLYKMNQQ-JOCQHMNTSA-N FC1=C(C=C2C=CC(=C(C2=C1F)OC)O)[C@@H]1CC[C@H](CC1)CCC Chemical compound FC1=C(C=C2C=CC(=C(C2=C1F)OC)O)[C@@H]1CC[C@H](CC1)CCC UPKSKMGLYKMNQQ-JOCQHMNTSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 2
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- 229910000104 sodium hydride Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- ODNBVEIAQAZNNM-UHFFFAOYSA-N 1-(6-chloroimidazo[1,2-b]pyridazin-3-yl)ethanone Chemical compound C1=CC(Cl)=NN2C(C(=O)C)=CN=C21 ODNBVEIAQAZNNM-UHFFFAOYSA-N 0.000 description 1
- XHEOXSQMBWJOKP-UHFFFAOYSA-N 1-(trifluoromethyl)-1$l^{3},2-benziodoxol-3-one Chemical compound C1=CC=C2I(C(F)(F)F)OC(=O)C2=C1 XHEOXSQMBWJOKP-UHFFFAOYSA-N 0.000 description 1
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 description 1
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- QVIKUAVXSRNDPS-UHFFFAOYSA-N 2-methoxynaphthalen-1-ol Chemical compound C1=CC=CC2=C(O)C(OC)=CC=C21 QVIKUAVXSRNDPS-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- DEXFNLNNUZKHNO-UHFFFAOYSA-N 6-[3-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperidin-1-yl]-3-oxopropyl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C1CCN(CC1)C(CCC1=CC2=C(NC(O2)=O)C=C1)=O DEXFNLNNUZKHNO-UHFFFAOYSA-N 0.000 description 1
- GUNJVIDCYZYFGV-UHFFFAOYSA-K Antimony trifluoride Inorganic materials F[Sb](F)F GUNJVIDCYZYFGV-UHFFFAOYSA-K 0.000 description 1
- YLBXDTPSEXCGHD-QAQDUYKDSA-N C(=O)C1=C(C2=CC=C(C=C2C=C1)[C@@H]1CC[C@H](CC1)CCC)CC Chemical compound C(=O)C1=C(C2=CC=C(C=C2C=C1)[C@@H]1CC[C@H](CC1)CCC)CC YLBXDTPSEXCGHD-QAQDUYKDSA-N 0.000 description 1
- WPYFLAMQWBGYBP-XUTJKUGGSA-N C(C1=CC=CC=C1)OC1=CC=C2C=C(C(=C(C2=C1)OCF)F)[C@@H]1CC[C@H](CC1)CCC Chemical compound C(C1=CC=CC=C1)OC1=CC=C2C=C(C(=C(C2=C1)OCF)F)[C@@H]1CC[C@H](CC1)CCC WPYFLAMQWBGYBP-XUTJKUGGSA-N 0.000 description 1
- ITAINSCLHDCLTM-DFPMAXHOSA-N C(CCC)OC1=CC=C2C=C(C=C(C2=C1)C(CF)F)[C@@H]1CC[C@H](CC1)CCC Chemical compound C(CCC)OC1=CC=C2C=C(C=C(C2=C1)C(CF)F)[C@@H]1CC[C@H](CC1)CCC ITAINSCLHDCLTM-DFPMAXHOSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- DBMVYMZDORXKPU-UHFFFAOYSA-N [CH2-]CC(CCC1)CCC1N Chemical compound [CH2-]CC(CCC1)CCC1N DBMVYMZDORXKPU-UHFFFAOYSA-N 0.000 description 1
- VMPVEPPRYRXYNP-UHFFFAOYSA-I antimony(5+);pentachloride Chemical compound Cl[Sb](Cl)(Cl)(Cl)Cl VMPVEPPRYRXYNP-UHFFFAOYSA-I 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 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
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- USLKCMBGQFYUFI-UHFFFAOYSA-N dichloromethane;tribromoborane Chemical compound ClCCl.BrB(Br)Br USLKCMBGQFYUFI-UHFFFAOYSA-N 0.000 description 1
- GRTGGSXWHGKRSB-UHFFFAOYSA-N dichloromethyl methyl ether Chemical compound COC(Cl)Cl GRTGGSXWHGKRSB-UHFFFAOYSA-N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- GRJJQCWNZGRKAU-UHFFFAOYSA-N pyridin-1-ium;fluoride Chemical compound F.C1=CC=NC=C1 GRJJQCWNZGRKAU-UHFFFAOYSA-N 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
本発明は電気光学的液晶表示材料として有用な、1-(トリフルオロメトキシ)ナフチル基を有する新規液晶性化合物、それを含む液晶組成物およびそれを用いた液晶表示素子に関する。 The present invention relates to a novel liquid crystalline compound having a 1- (trifluoromethoxy) naphthyl group, a liquid crystal composition containing the same, and a liquid crystal display device using the same, useful as an electro-optical liquid crystal display material.
液晶表示素子は、低電圧作動、薄型表示等の優れた特徴から現在広く用いられている。従来の液晶表示素子の表示方式にはTN(ねじれネマチック)、STN(超ねじれネマチック)、またはTNをベースにしたアクティブマトリックス(TFT:薄膜トランジスタ)等があり、これらは誘電率異方性値が正の液晶組成物を利用するものである。しかし、これら表示方式の欠点の一つとして視野角の狭さがあり、近年高まっている液晶パネルの大型化の要求に伴い、その改善が大きな課題となっている。 Liquid crystal display elements are currently widely used because of their excellent features such as low voltage operation and thin display. Conventional liquid crystal display device display methods include TN (twisted nematic), STN (super twisted nematic), or active matrix (TFT: thin film transistor) based on TN, which has a positive dielectric anisotropy value. The liquid crystal composition is used. However, one of the disadvantages of these display methods is a narrow viewing angle, and with the increasing demand for larger liquid crystal panels in recent years, the improvement has become a major issue.
この解決策として近年、垂直配向方式、IPS(インプレインスイッチング)等の表示方式が新たに実用化されてきた。垂直配向方式は液晶分子の垂直配向を利用して視野角の改善を図った方式であり、誘電率異方性(Δε)が負の液晶組成物が使用される。またIPSは、ガラス基板に対して水平方向の横電界を用いて液晶分子をスイッチングさせることで視野角の改善を図った方法であり、Δεが正または負の液晶組成物が使用される。このように、視野角改善のために有効な表示方式である垂直配向方式およびIPSにはΔεが負である液晶化合物ならびに液晶組成物が必要であり、強く要望されるようになってきた。従来、Δεが負の液晶組成物は、2,3-ジフルオロフェニレン基を有する化合物が主として用いられてきた(特許文献1)。しかしながら、この化合物を用いた液晶組成物はΔεの絶対値が十分大きくない問題を有していた(特許文献2)。 In recent years, display methods such as vertical alignment and IPS (in-plane switching) have been put to practical use as a solution. The vertical alignment method is a method in which the viewing angle is improved by utilizing the vertical alignment of liquid crystal molecules, and a liquid crystal composition having a negative dielectric anisotropy (Δε) is used. IPS is a method in which viewing angle is improved by switching liquid crystal molecules using a horizontal electric field in the horizontal direction with respect to a glass substrate, and a liquid crystal composition having a positive or negative Δε is used. As described above, the vertical alignment method and the IPS, which are effective display methods for improving the viewing angle, require a liquid crystal compound and a liquid crystal composition having a negative Δε, and have been strongly demanded. Conventionally, a compound having a 2,3-difluorophenylene group has been mainly used for a liquid crystal composition having a negative Δε (Patent Document 1). However, a liquid crystal composition using this compound has a problem that the absolute value of Δε is not sufficiently large (Patent Document 2).
そこで、2,3-ジフルオロフェニレン基を有する化合物より絶対値の大きい負のΔεを有する化合物としてトリフルオロナフタレン誘導体が報告されている(特許文献3)。しかしながら、液晶表示素子においてより消費電力を低減する要求は強く、トリフルオロナフタレン骨格を用いてもなお、Δεの絶対値が十分大きいとは言えない問題を有していた。 Therefore, a trifluoronaphthalene derivative has been reported as a compound having a negative Δε having a larger absolute value than a compound having a 2,3-difluorophenylene group (Patent Document 3). However, there is a strong demand for reducing power consumption in the liquid crystal display element, and even if a trifluoronaphthalene skeleton is used, there is a problem that the absolute value of Δε cannot be said to be sufficiently large.
一方、ベンゼン環の側方にトリフルオロメトキシ基を有する化合物は報告されている(特許文献４)。更に当該引用文献記載の化合物は、大きな負のΔεを有する液晶組成物の成分として有利に使用できることも報告されている。しかしながら、ベンゼン環の側方にトリフルオロメトキシ基を有した化合物は、次のようなことから誘電率異方性の絶対値が十分大きくならない問題を有している。すなわち、負のΔεを有する化合物において、Δεの絶対値を大きくするためには、電子吸引性の大きい置換基を側方に置換する必要がある。しかし、１，４−フェニレン基においては側方置換位置は２位および３位のニ箇所しかなく、Δεの絶対値を増大することには限界がある。又、ビフェニル骨格のように１，４−フェニレン基を連結した構造においては、二つのフェニレン基に置換した電子吸引性基が同じ方向を向く可能性は低くΔεの絶対値は増大しないことが一般的である。 On the other hand, a compound having a trifluoromethoxy group on the side of the benzene ring has been reported (Patent Document 4). Furthermore, it has been reported that the compound described in the cited document can be advantageously used as a component of a liquid crystal composition having a large negative Δε. However, a compound having a trifluoromethoxy group on the side of the benzene ring has a problem that the absolute value of dielectric anisotropy is not sufficiently increased due to the following. That is, in a compound having a negative Δε, in order to increase the absolute value of Δε, a substituent having a high electron-withdrawing property must be substituted laterally. However, in the 1,4-phenylene group, there are only two side substitution positions at the 2nd and 3rd positions, and there is a limit to increasing the absolute value of Δε. In addition, in a structure in which 1,4-phenylene groups are linked as in the biphenyl skeleton, the electron-withdrawing group substituted with two phenylene groups is unlikely to be in the same direction, and the absolute value of Δε generally does not increase. Is.
以上のように、Δεが負の化合物において、より大きいΔεの絶対値を有する化合物の開発が望まれている。 As described above, it is desired to develop a compound having a larger absolute value of Δε in a compound having a negative Δε.
本発明が解決しようとする課題は、Δεが負の化合物において、より大きいΔεの絶対値を有する化合物を提供し、また当該化合物を用いた実用的な液晶組成物を提供することにある。 The problem to be solved by the present invention is to provide a compound having a larger absolute value of Δε in a compound having a negative Δε, and to provide a practical liquid crystal composition using the compound.
本発明は、上記課題を解決するための手段として、一般式(I) The present invention provides a general formula (I) as a means for solving the above problems.
(式中、R1およびR2は、それぞれ独立的に炭素数1〜12のアルキル基、炭素数2〜12のアルケニル基、炭素数1〜12のアルコキシル基または炭素数2〜12のアルケニルオキシ基を表し、それぞれの1個以上の水素原子は独立的にフッ素原子に置換されていてもよく、またそれぞれの-CH2-基は独立的に-O-、-S-、-CO-、-COO-、-OCO-または-OCOO-に置換されていてもよく、
A1、A2、B1およびB2は、それぞれ独立的にトランス-1,4-シクロヘキシレン基、トランス-1,3-ジオキサン-2,5-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基または1個以上の水素原子がフッ素原子に置換されていてもよい1,4-フェニレン基を表し、
L1、L2、M1およびM2は、それぞれ独立的に単結合、-CH2CH2-、-CH=CH-、-CH≡CH-、-OCH2-、-CH2O-、-OCF2-、-CF2O-、-CF2CF2-、-CF=CF-、-OCO-、-COO-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-COS-または-SCO-を表し、
X1およびX2は、それぞれ独立的に水素原子またはフッ素原子を表し、
p、q、rおよびsは、それぞれ独立的に0または1を表す。)で表される1-(トリフルオロメトキシ)ナフタレン誘導体を提供し、一般式(I)で表される化合物を1種または2種以上含有することを特徴とする液晶組成物、更に、当該液晶組成物を構成要素とする液晶素子を提供する。
(In the formula, R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or an alkenyloxy group having 2 to 12 carbon atoms. Each of one or more hydrogen atoms may be independently substituted with fluorine atoms, and each —CH 2 — group may independently be —O—, —S—, —CO—, May be substituted by -COO-, -OCO- or -OCOO-
A 1 , A 2 , B 1 and B 2 are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, pyridine-2,5-diyl group Represents a pyrimidine-2,5-diyl group or a 1,4-phenylene group in which one or more hydrogen atoms may be substituted with fluorine atoms,
L 1 , L 2 , M 1 and M 2 are each independently a single bond, —CH 2 CH 2 —, —CH═CH—, —CH≡CH—, —OCH 2 —, —CH 2 O—, -OCF 2- , -CF 2 O-, -CF 2 CF 2- , -CF = CF-, -OCO-, -COO-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 ) -, -CH (CH 3 ) CH (CH 3 )-, -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-,- O (CH 2 ) 3- , -COS- or -SCO-
X 1 and X 2 each independently represent a hydrogen atom or a fluorine atom,
p, q, r and s each independently represent 0 or 1. 1)-(trifluoromethoxy) naphthalene derivative represented by formula (I), a liquid crystal composition characterized by containing one or more compounds represented by general formula (I), and the liquid crystal A liquid crystal device comprising a composition as a constituent element is provided.
本願発明の液晶化合物は、ナフタレン環の１位に電子吸引性の非常に大きいトリフルオロメトキシ基が置換されていることに特徴を有する。そのため、この骨格を有する液晶化合物は分子の短軸方向に大きな分極を有することとなり、結果として絶対値の大きい負の誘電率異方性を有するものである。 The liquid crystal compound of the present invention is characterized in that a trifluoromethoxy group having a very high electron-withdrawing property is substituted at the 1-position of the naphthalene ring. Therefore, the liquid crystal compound having this skeleton has a large polarization in the minor axis direction of the molecule, and as a result, has a negative dielectric anisotropy having a large absolute value.
本発明の一般式(I)で表される化合物は、Δεが負であって極めて大きい絶対値を有する。更に、熱、光、水等に対し、化学的に安定であり、現在汎用されている液晶化合物あるいは液晶組成物との相溶性に優れているため、低電圧駆動が可能である実用的な液晶組成物の成分として適している。 In the compound represented by the general formula (I) of the present invention, Δε is negative and has an extremely large absolute value. In addition, it is chemically stable to heat, light, water, etc., and has excellent compatibility with currently used liquid crystal compounds or liquid crystal compositions, so that it can be driven at a low voltage. Suitable as a component of the composition.
一般式(I)において、R1およびR2は、それぞれ独立的に炭素数1〜12のアルキル基、炭素数2〜12のアルケニル基、炭素数1〜12のアルコキシル基または炭素数2〜12のアルケニルオキシ基を表し、それぞれの1個以上の水素原子は独立的にフッ素原子に置換されていてもよく、またそれぞれの-CH2-基は独立的に-O-、-S-、-CO-、-COO-、-OCO-または-OCOO-に置換されていてもよいが、炭素数1〜8のアルキル基、炭素数2〜8のアルケニル基、炭素数1〜7のアルコキシル基または炭素数2〜7のアルケニルオキシ基が好ましく、炭素原子数2〜5の直鎖状アルキル基、ビニル基、3-ブテニル基、トランス-1-プロペン-1-イル基またはトランス-3-ペンテン-1-イル基がより好ましい。 In general formula (I), R 1 and R 2 are each independently an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, an alkoxyl group having 1 to 12 carbon atoms, or 2 to 12 carbon atoms. Each of one or more hydrogen atoms may be independently substituted with fluorine atoms, and each —CH 2 — group may independently be —O—, —S—, — Optionally substituted by CO-, -COO-, -OCO- or -OCOO-, but an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxyl group having 1 to 7 carbon atoms or An alkenyloxy group having 2 to 7 carbon atoms is preferable, a linear alkyl group having 2 to 5 carbon atoms, a vinyl group, a 3-butenyl group, a trans-1-propen-1-yl group, or trans-3-pentene- A 1-yl group is more preferred.
A1、A2、B1およびB2は、それぞれ独立的にトランス-1,4-シクロヘキシレン基、トランス-1,3-ジオキサン-2,5-ジイル基、ピリジン-2,5-ジイル基、ピリミジン-2,5-ジイル基または1個以上の水素原子がフッ素原子に置換されていてもよい1,4-フェニレン基を表すが、トランス-1,4-シクロヘキシレン基または1個以上の水素原子がフッ素原子に置換されていてもよい1,4-フェニレン基が好ましく、トランス-1,4-シクロヘキシレン基または無置換の1,4-フェニレン基がより好ましい。 A 1 , A 2 , B 1 and B 2 are each independently trans-1,4-cyclohexylene group, trans-1,3-dioxane-2,5-diyl group, pyridine-2,5-diyl group Represents a pyrimidine-2,5-diyl group or a 1,4-phenylene group in which one or more hydrogen atoms may be substituted by a fluorine atom, but a trans-1,4-cyclohexylene group or one or more A 1,4-phenylene group in which a hydrogen atom may be substituted with a fluorine atom is preferable, and a trans-1,4-cyclohexylene group or an unsubstituted 1,4-phenylene group is more preferable.
L1、L2、M1およびM2は、それぞれ独立的に単結合、-CH2CH2-、-CH=CH-、-CH≡CH-、-OCH2-、-CH2O-、-OCF2-、-CF2O-、-CF2CF2-、-CF=CF-、-OCO-、-COO-、-CH(CH3)CH2-、-CH2CH(CH3)-、-CH(CH3)CH(CH3)-、-OCH(CH3)-、-CH(CH3)O-、-(CH2)4-、-(CH2)3O-、-O(CH2)3-、-COS-または-SCO-を表すが、それぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-、-CF2O-または-CF2CF2-であることが好ましく、単結合または-CH2CH2-であることがより好ましい。 L 1 , L 2 , M 1 and M 2 are each independently a single bond, —CH 2 CH 2 —, —CH═CH—, —CH≡CH—, —OCH 2 —, —CH 2 O—, -OCF 2- , -CF 2 O-, -CF 2 CF 2- , -CF = CF-, -OCO-, -COO-, -CH (CH 3 ) CH 2- , -CH 2 CH (CH 3 ) -, -CH (CH 3 ) CH (CH 3 )-, -OCH (CH 3 )-, -CH (CH 3 ) O-,-(CH 2 ) 4 -,-(CH 2 ) 3 O-,- Represents O (CH 2 ) 3- , -COS- or -SCO-, but each independently represents a single bond, -CH 2 CH 2- , -OCH 2- , -CH 2 O-, -OCF 2 -,- CF 2 O— or —CF 2 CF 2 — is preferable, and a single bond or —CH 2 CH 2 — is more preferable.
X1およびX2は、それぞれ独立的に水素原子またはフッ素原子を表すが、Δεをより大きくするためには、X1およびX2がそれぞれフッ素原子であることが好ましい。 X 1 and X 2 each independently represent a hydrogen atom or a fluorine atom, but in order to increase Δε, X 1 and X 2 are each preferably a fluorine atom.
p、q、rおよびsは、0または1を表すが、p+q+r+sが1以上かつ3以下の整数であることが好ましく、p+q+r+sが1または2であることがより好ましい。 p, q, r and s represent 0 or 1, but p + q + r + s is preferably an integer of 1 or more and 3 or less, and p + q + r + s is 1 or 2 It is more preferable.
上述のように一般式(I)の化合物はそのR1、R2、A1、A2、B1、B2、L1、L2、M1、M2、X1、X2、p、q、rおよびsの選択により多種の化合物を包含しうるわけであるが、これらの中では以下の一般式(I-a-a)〜一般式(I-h-k)で表される各化合物が好ましい。 As mentioned above, the compounds of general formula (I) are R 1 , R 2 , A 1 , A 2 , B 1 , B 2 , L 1 , L 2 , M 1 , M 2 , X 1 , X 2 , p A variety of compounds can be included depending on the selection of q, r, and s. Among these, compounds represented by the following general formulas (Iaa) to (Ihk) are preferable.
（式中、R1およびR2は、それぞれ独立的に炭素数1〜8のアルキル基、炭素数2〜8のアルケニル基、炭素数1〜7のアルコキシル基または炭素数2〜7のアルケニルオキシ基を表す。）
さらに、上式中では一般式(I-a-a)〜一般式(I-a-d)、一般式(I-b-c)〜一般式(I-b-e)、一般式(I-c-a)〜一般式(I-c-e)、一般式(I-d-c)〜一般式(I-d-d)の各化合物が特に好ましい。
Wherein R 1 and R 2 are each independently an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, an alkoxyl group having 1 to 7 carbon atoms or an alkenyloxy having 2 to 7 carbon atoms. Represents a group.)
Further, in the above formula, general formula (Iaa) to general formula (Iad), general formula (Ibc) to general formula (Ibe), general formula (Ica) to general formula (Ice), general formula (Idc) to general formula Each compound of (Idd) is particularly preferred.
本発明の(I)の化合物は、例えば、以下のようにして製造することができる。 The compound (I) of the present invention can be produced, for example, as follows.
一般式(II) Formula (II)
(式中、R1、R2、A1、A2、B1、B2、L1、L2、M1、M2、X1、X2、p、q、rおよびsは一般式(I)におけると同じ意味を表す。)で表される1-ナフトール誘導体に、水酸化ナトリウム、水酸化カリウム、金属ナトリウム、金属カリウム、水素化ナトリウム等の塩基存在下、二硫化炭素および1-ヨードアルカンを作用させることによりキサントゲン酸エステル誘導体(III) (In the formula, R 1 , R 2 , A 1 , A 2 , B 1 , B 2 , L 1 , L 2 , M 1 , M 2 , X 1 , X 2 , p, q, r and s are general formulas. In the presence of a base such as sodium hydroxide, potassium hydroxide, metallic sodium, metallic potassium, sodium hydride, etc., the 1-naphthol derivative represented by (I) represents the same meaning as in (I). Xanthate derivatives (III) by the action of iodoalkanes
(式中、R3は炭素数1〜8のアルキル基を表し、R1、R2、A1、A2、B1、B2、L1、L2、M1、M2、X1、X2、p、q、rおよびsは一般式(I)におけると同じ意味を表す。)を得る。得られた化合物(III)を、ジクロロメタン等のハロゲン溶媒中、N-ブロモコハク酸イミド、N,N-ジブロモヒダントインなどの酸化剤存在下、フッ化水素ピリジン錯体を作用させることにより、一般式(I)で表される化合物を得ることができる。 (Wherein R 3 represents an alkyl group having 1 to 8 carbon atoms, R 1 , R 2 , A 1 , A 2 , B 1 , B 2 , L 1 , L 2 , M 1 , M 2 , X 1 , X 2 , p, q, r and s have the same meaning as in general formula (I). The obtained compound (III) is reacted with a hydrogen fluoride pyridine complex in a halogen solvent such as dichloromethane in the presence of an oxidizing agent such as N-bromosuccinimide and N, N-dibromohydantoin to give a general formula (I ) Can be obtained.
あるいは、1-ナフトール誘導体(II) に、水酸化ナトリウム、水酸化カリウム、金属ナトリウム、金属カリウム、水素化ナトリウム等の塩基存在下、四塩化炭素を作用させることによりトリクロロメトキシナフタレン誘導体(IV) Alternatively, trichloromethoxynaphthalene derivative (IV) can be obtained by allowing carbon tetrachloride to act on 1-naphthol derivative (II) in the presence of a base such as sodium hydroxide, potassium hydroxide, metallic sodium, metallic potassium or sodium hydride.
(式中、R1、R2、A1、A2、B1、B2、L1、L2、M1、M2、X1、X2、p、q、rおよびsは一般式(I)におけると同じ意味を表す。)を得る。得られた化合物(IV)を、五塩化アンチモン存在下、三フッ化アンチモンを作用させることにより、一般式(I)で表される化合物を得ることもできる。 (In the formula, R 1 , R 2 , A 1 , A 2 , B 1 , B 2 , L 1 , L 2 , M 1 , M 2 , X 1 , X 2 , p, q, r and s are general formulas. Represents the same meaning as in (I)). The compound represented by the general formula (I) can also be obtained by reacting the obtained compound (IV) with antimony trifluoride in the presence of antimony pentachloride.
あるいは、トリクロロメトキシナフタレン誘導体(IV)に無水フッ化水素酸を作用させることにより、一般式(I)で表される化合物を得ることもできる。 Alternatively, the compound represented by the general formula (I) can also be obtained by allowing anhydrous hydrofluoric acid to act on the trichloromethoxynaphthalene derivative (IV).
あるいは、1-ナフトール誘導体(II)を四塩化炭素中、無水フッ化水素酸を直接作用させることにより、一般式(I)で表される化合物を得ることもできる。 Alternatively, the 1-naphthol derivative (II) can be directly reacted with anhydrous hydrofluoric acid in carbon tetrachloride to obtain a compound represented by the general formula (I).
あるいは、1-ナフトール誘導体(II)にS-トリフルオロメチル塩などの梅本試薬あるいは高原子ヨウ素化トリフルオロメチル塩などのトニ試薬を作用させることにより、一般式(I)で表される化合物を得ることができる。 Alternatively, by reacting 1-naphthol derivative (II) with Umemoto reagent such as S-trifluoromethyl salt or Toni reagent such as high atom iodinated trifluoromethyl salt, the compound represented by general formula (I) can be obtained. Can be obtained.
一般式(I)で表される化合物の多くは、他の液晶材料に対し比較的優れた相溶性を示す。また、高い比抵抗や電圧保持率を得ることも容易である。従って、他の液晶化合物との混合物の状態で液晶表示セル用材料として、好適に用いることができる。一般式(I)で表される化合物はその添加によりΔεの絶対値を大きく増大させてその閾値電圧を低減することが可能であり、かつ高速応答と、屈折率異方性(Δn)の増大が可能であるといった特長を併せ持ち、前述の各種表示方式のいずれにおいても使用可能であるが、単純マトリックス駆動あるいはアクティブマトリックス駆動のTN型表示素子、およびSTN表示素子に用いることが適しており、特にアクティブマトリックス駆動のTN表示素子の液晶材料の極性成分として用いることが好ましい。 Many of the compounds represented by the general formula (I) exhibit relatively excellent compatibility with other liquid crystal materials. It is also easy to obtain a high specific resistance and voltage holding ratio. Therefore, it can be suitably used as a liquid crystal display cell material in a mixture with other liquid crystal compounds. By adding the compound represented by the general formula (I), the absolute value of Δε can be greatly increased to reduce the threshold voltage, and the high-speed response and the refractive index anisotropy (Δn) are increased. It can be used in any of the above-mentioned various display methods, but is suitable for use in simple matrix drive or active matrix drive TN type display elements and STN display elements. It is preferably used as a polar component of a liquid crystal material of an active matrix driven TN display element.
このように、一般式(I)で表される化合物と混合して使用することのできるネマチック液晶化合物の好ましい代表例としては、本発明の提供する組成物においては、その第1成分として一般式(I)で表される化合物を少なくとも1種含有するが、その他の成分として特に以下の一般式(A) Thus, as a preferred representative example of a nematic liquid crystal compound that can be used by mixing with the compound represented by the general formula (I), in the composition provided by the present invention, the first component is represented by the general formula It contains at least one compound represented by (I), but as other components, in particular the following general formula (A)
(式中、Rcは炭素原子数1〜7の直鎖状アルキル基またはアルケニル基を表し、Rdは炭素原子数1〜12の直鎖状アルキル基、アルケニル基、アルコキシル基またはアルケニルオキシ基を表し、p3は0または1を表し、MbおよびMcはそれぞれ独立的に単結合、-COO-または-CH2CH2-を表し、Gcはトランス-1,4-シクロヘキシレン基または-1,4-フェニレン基を表す。)で表される化合物の1種または2種以上を含有することが好ましい。 (In the formula, R c represents a linear alkyl group or alkenyl group having 1 to 7 carbon atoms, and R d represents a linear alkyl group, alkenyl group, alkoxyl group or alkenyloxy group having 1 to 12 carbon atoms. P3 represents 0 or 1, M b and M c each independently represents a single bond, —COO— or —CH 2 CH 2 —, and G c represents a trans-1,4-cyclohexylene group or It preferably represents one or more of the compounds represented by -1,4-phenylene group.
一般式(A)において、Rcは炭素原子数2〜7の直鎖状アルキル基、炭素原子数2〜5の1-アルケニル基または炭素原子数4〜5の3-アルケニル基が好ましく、直鎖状アルキル基としてはエチル基、プロピル基、ブチル基またはペンチル基がより好ましく、1-アルケニル基としてはビニル基またはトランス-1-プロペニル基がより好ましく、3-アルケニル基としては3-ブテニル基またはトランス-3-ペンテニル基がより好ましい。Rdは炭素原子数1〜7の直鎖状アルキル基、炭素原子数2〜5の1-アルケニル基、炭素原子数4〜5の3-アルケニル基、炭素原子数1〜3の直鎖状アルコキシル基が好ましい。Mbが存在する場合には、MbおよびMcの少なくとも一方は単結合が好ましい。 In the general formula (A), R c is preferably a linear alkyl group having 2 to 7 carbon atoms, a 1-alkenyl group having 2 to 5 carbon atoms, or a 3-alkenyl group having 4 to 5 carbon atoms. The chain alkyl group is more preferably an ethyl group, propyl group, butyl group or pentyl group, the 1-alkenyl group is more preferably a vinyl group or a trans-1-propenyl group, and the 3-alkenyl group is a 3-butenyl group. Or a trans-3-pentenyl group is more preferable. R d is a linear alkyl group having 1 to 7 carbon atoms, a 1-alkenyl group having 2 to 5 carbon atoms, a 3-alkenyl group having 4 to 5 carbon atoms, or a linear chain having 1 to 3 carbon atoms. Alkoxyl groups are preferred. If the M b is present, at least one of M b and M c is a single bond.
一般式(A)で表される化合物としては以下の一般式(A-1)〜一般式(A-14)で表される化合物が好ましく、一般式(A-1)、一般式(A-2)、一般式(A-3)、一般式(A-5)または一般式(A-6)で表される化合物が特に好ましい。 As the compound represented by the general formula (A), compounds represented by the following general formula (A-1) to general formula (A-14) are preferable, and the general formula (A-1), the general formula (A- The compound represented by 2), general formula (A-3), general formula (A-5) or general formula (A-6) is particularly preferred.
（式中、RAおよびRBはそれぞれ独立的に炭素原子数1〜7の直鎖状アルキル基、炭素原子数2〜3の1-アルケニル基または炭素原子数4〜5の3-アルケニル基を表し、RCは炭素原子数1〜5の直鎖状アルキル基または炭素原子数3〜4の直鎖状2-アルケニル基を表し、RDは炭素原子数1〜3の直鎖状アルキル基または炭素原子数4〜5の3-アルケニル基を表し、REは炭素原子数1〜3の直鎖状アルキル基または炭素原子数3〜4の直鎖状2-アルケニル基を表す。）
本発明の液晶組成物において一般式(B)
Wherein R A and R B are each independently a linear alkyl group having 1 to 7 carbon atoms, a 1-alkenyl group having 2 to 3 carbon atoms, or a 3-alkenyl group having 4 to 5 carbon atoms. R C represents a linear alkyl group having 1 to 5 carbon atoms or a linear 2-alkenyl group having 3 to 4 carbon atoms, and RD represents a linear alkyl group having 1 to 3 carbon atoms. Group or a 4-alkenyl group having 4 to 5 carbon atoms, and R E represents a linear alkyl group having 1 to 3 carbon atoms or a linear 2-alkenyl group having 3 to 4 carbon atoms.)
In the liquid crystal composition of the present invention, the general formula (B)
(式中、Reは炭素原子数1〜7のアルキル基を表し、Rfは炭素原子数1〜7の直鎖状アルキル基、アルコキシル基またはアルケニルオキシ基を表し、p4は0または1を表し、MdおよびMeはそれぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-、-CF2O-または-COO-を表し、Gdはトランス-1,4-シクロヘキシレン基あるいは1〜2個の水素原子がフッ素により置換されていてもよい-1,4-フェニレン基を表す。)で表される2,3-ジフルオロ-1,4-フェニレン誘導体の1種または2種以上を含有していても良い。 (Wherein R e represents an alkyl group having 1 to 7 carbon atoms, R f represents a linear alkyl group having 1 to 7 carbon atoms, an alkoxyl group or an alkenyloxy group, and p4 represents 0 or 1) M d and Me each independently represent a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, —OCF 2 —, —CF 2 O— or —COO—, G d represents a trans-1,4-cyclohexylene group or a 1,4-phenylene group in which 1 to 2 hydrogen atoms may be substituted with fluorine. One or more of 1,4-phenylene derivatives may be contained.
一般式(B)において、Reは炭素原子数2〜7の直鎖状アルキル基が好ましい。Rfは炭素原子数1〜5の直鎖状アルキル基、直鎖状アルコキシル基が好ましく、炭素原子数1〜4の直鎖状アルキル基または炭素原子数1〜4の直鎖状アルコキシル基が特に好ましい。MdおよびMeのうち一方は単結合であることが好ましく、他方は単結合、-CH2CH2-または-COO-であることが好ましい。 In the general formula (B), R e is preferably a linear alkyl group having 2 to 7 carbon atoms. R f is preferably a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxyl group, and a linear alkyl group having 1 to 4 carbon atoms or a linear alkoxyl group having 1 to 4 carbon atoms. Particularly preferred. Preferably one of the M d and M e is a single bond and the other is a single bond, -CH 2 CH 2 - is preferred or -COO- in which.
一般式(B)には非常に多くの化合物が含まれるが、以下の一般式(B-1)〜一般式(B-9)で表される化合物が好ましい。 The general formula (B) includes a large number of compounds, but compounds represented by the following general formulas (B-1) to (B-9) are preferable.
上式中、RFは炭素原子数1〜7の直鎖状アルキル基を表し、RGは炭素原子数1〜5の直鎖状アルキル基または炭素原子数1〜4の直鎖状アルコキシル基を表す。 In the above formula, R F represents a linear alkyl group having 1 to 7 carbon atoms, and RG represents a linear alkyl group having 1 to 5 carbon atoms or a linear alkoxyl group having 1 to 4 carbon atoms. Represents.
また、本発明の液晶組成物において、一般式(C)〜一般式(G) Further, in the liquid crystal composition of the present invention, the general formula (C) ~ general formula (G)
(式中、Rg、Ri、RkおよびRmは炭素原子数1〜7の直鎖状アルキル基を表し、Rh、Rj、およびRnは炭素原子数1〜7の直鎖状アルキル基、アルコキシル基またはアルケニルオキシ基を表し、Rlは炭素原子数1〜7の直鎖状アルキル基を表し、Roは炭素原子数1〜7の直鎖状アルキル基、アルコキシル基または炭素原子数2〜7の直鎖状アルケニル基、アルケニルオキシ基を表し、Rpは炭素原子数1〜7の直鎖状アルキル基または炭素原子数2〜7の直鎖状アルケニル基を表し、XaおよびXbは水素原子またはフッ素原子を表し、p5、p6、p7およびp8はそれぞれ独立的に0または1を表し、p9およびp10はそれぞれ独立的に0、1または2を表し、p9およびp10の合計は1または2であり、MfおよびMg、MhおよびMi、MjおよびMk、MlおよびMm、Mnはそれぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-、-CF2O-または-COO-を表し、Moは単結合または-CH2CH2-を表し、Ge、Gf、Gg、Gh、GiおよびGjはそれぞれ独立的にトランス-1,4-シクロヘキシレン基あるいは1〜2個の水素原子がフッ素により置換されていてもよい-1,4-フェニレン基を表し、Gi、Gj、MnおよびMoが複数存在する場合、それらは同一であっても異なっていてもよい。)で表される化合物の1種または2種以上を含有していても良い。 (Wherein R g , R i , R k and R m represent a linear alkyl group having 1 to 7 carbon atoms, and R h , R j and R n are linear chains having 1 to 7 carbon atoms. Represents a linear alkyl group, an alkoxyl group or an alkenyloxy group, R 1 represents a linear alkyl group having 1 to 7 carbon atoms, and R o represents a linear alkyl group having 1 to 7 carbon atoms, an alkoxyl group or A linear alkenyl group having 2 to 7 carbon atoms, an alkenyloxy group, R p represents a linear alkyl group having 1 to 7 carbon atoms or a linear alkenyl group having 2 to 7 carbon atoms, X a and X b represent a hydrogen atom or a fluorine atom, p5, p6, p7 and p8 each independently represent 0 or 1, p9 and p10 each independently represent 0, 1 or 2, p9 and The sum of p10 is 1 or 2, and M f and M g , M h and M i , M j and M k , M l and M m , and M n are each independently a single bond, —CH 2 CH 2 -, - OCH 2 -, - CH 2 O -, - OCF 2 -, - CF 2 O- or -COO- the stands, M o is a single bond or represents -CH 2 CH 2 -, G e, G f , G g , G h , G i and G j are each independently a trans-1,4-cyclohexylene group or a 1,4-phenylene group in which 1 to 2 hydrogen atoms may be substituted by fluorine And when there are a plurality of G i , G j , M n and Mo , they may be the same or different.) And contain one or more of the compounds represented by May be.
一般式(C)〜一般式(G)において、Rg、Ri、Rk、RmおよびRpは炭素原子数2〜7の直鎖状アルキル基が好ましい。Rh、Rj、RnおよびRoは炭素原子数1〜5の直鎖状アルキル基、直鎖状アルコキシル基が好ましい。Rlは炭素原子数1〜3の直鎖状アルキル基が好ましい。MfおよびMg、MhおよびMi、MjおよびMk、MlおよびMmはそれぞれ独立的に単結合、-CH2CH2-、-OCH2-、-CH2O-、-OCF2-、-CF2O-または-COO-を表すが、一方は単結合であることが好ましく、他方は単結合、-CH2CH2-または-COO-であることが好ましい。Mnは単結合、-CH2CH2-、-CH2O-または-CF2O-が好ましい。 In the general formula (C) to the general formula (G), R g , R i , R k , R m and R p are preferably linear alkyl groups having 2 to 7 carbon atoms. R h , R j , R n and R o are preferably a linear alkyl group having 1 to 5 carbon atoms and a linear alkoxyl group. R l is preferably a linear alkyl group having 1 to 3 carbon atoms. M f and M g , M h and M i , M j and M k , M l and M m are each independently a single bond, —CH 2 CH 2 —, —OCH 2 —, —CH 2 O—, — OCF 2 —, —CF 2 O— or —COO— is represented, and one is preferably a single bond, and the other is preferably a single bond, —CH 2 CH 2 — or —COO—. M n is preferably a single bond, —CH 2 CH 2 —, —CH 2 O— or —CF 2 O—.
以下に本発明の実施例を示し、本発明を更に説明する。しかし、本発明はこれらの実施例に限定されるものではない。 The following examples further illustrate the present invention. However, the present invention is not limited to these examples.
なお、相転移温度の測定は温度調節ステージを備えた偏光顕微鏡および示差走査熱量計(DSC)を併用して行った。また、化合物の構造は核磁気共鳴スペクトル(NMR)、赤外共鳴スペクトル(IR)、質量スペクトル(MS)等により確認した。
（実施例１）7-ブトキシ-1,2-ジフルオロ-3-[2-(トランス-4-プロピルシクロヘキシル)エチル]-8-(トリフルオロメトキシ)ナフタレン(I-1)の合成
The phase transition temperature was measured using a polarizing microscope equipped with a temperature control stage and a differential scanning calorimeter (DSC). The structure of the compound was confirmed by nuclear magnetic resonance spectrum (NMR), infrared resonance spectrum (IR), mass spectrum (MS) and the like.
Example 1 Synthesis of 7-butoxy-1,2-difluoro-3- [2- (trans-4-propylcyclohexyl) ethyl] -8- (trifluoromethoxy) naphthalene (I-1)
（実施例1-1）7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)エチル-2-ナフトール
(以下、ドラフト中で行う。)7-ブトキシ-1,2-ジフルオロ-3-(トランス-4-プロピルシクロヘキシル)エチルナフタレン(22.0 g、0.056 mol)のジクロロメタン(220 ml)溶液中に、1.0 M三臭化ホウ素ジクロロメタン溶液(86 ml、0.086 mol)を加えた後、室温で24時間攪拌した。水を滴下して加えた後、室温で0.5時間攪拌した。有機層を分離し、水層からジクロロメタンで抽出した。有機層を合わせた後、5%炭酸水素ナトリウム水溶液、飽和食塩水の順で洗條し、無水硫酸ナトリウムで乾燥した。塩を濾別後、溶媒を留去し、薄黄色の固体(19.0 g)を得た。(収率 定量的)
（実施例1-2）7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)エチル-2-ナフトール
(以下、ドラフト中で行う。)7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)エチル-2-ナフトール(19.0 g、0.057 mol)のジクロロメタン(475 ml)溶液を5~10℃に冷却しながら激しく攪拌している中に、ジクロロメチルメチルエーテル(14.5 ml、0.164 mol)を加えた後、さらに内温を5~10℃に保ちながら、続けて塩化チタン(IV)(24 ml、0.219 mol)のジクロロメタン(50 ml)溶液を0.5時間かけて滴下して加えた後、内温を5~10℃に保ちながら1時間攪拌した。反応液を氷水に滴下して加えて反応を停止させた後、室温で0.5時間攪拌した。有機層を分離し、水層からジクロロメタンで抽出した。有機層を合わせた後、5%炭酸水素ナトリウム水溶液、飽和食塩水の順で洗條し、無水硫酸ナトリウムで乾燥した。塩を濾別後、溶媒を留去し、褐色の固体を得た。得られた固体を再結晶(ジクロロメタン、メタノール)することにより、赤桃色の粉末(15.2 g)を得た。(収率 73.0%)
（実施例1-3）2-ブトキシ-7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)エチルナフタレン
(以下、窒素雰囲気下で行う。) 7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)エチル-2-ナフトール(18.6 g、0.051 mol)と無水炭酸カリウム(14.1 g、0.102 mol)をN,N-ジメチルホルムアミド(DMF、200 ml)懸濁液を室温で0.5時間激しく攪拌した。1-ブロモブタン(9.0 g、0.066 mol)を加えた後、6時間加熱還流し、室温まで放冷した。反応液を水に加えて反応を停止させた後、析出した固体をトルエンに溶解させた。有機層を分離し、水層をトルエンで抽出した。有機層を合わせた後、飽和食塩水で洗條し、そのままカラム(シリカゲル)を通過させ、さらにトルエンを用いてカラムを洗滌した。有機層を合わせた後、溶媒を留去することにより、褐色の液体を得た。得られた液体を減圧蒸留し、淡黄色の液体を得た。さらに得られた液体を再結晶(酢酸エチル、メタノール)することにより、薄赤色の固体(18.6 g)を得た。(収率 86.1%)
（実施例1-4）2-ブトキシ-7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)エチル-1-ナフトール
(以下、ドラフト中で行う。) ホウ酸(12.7 g、0.205 mol)のテトラヒドロフラン(180 ml)懸濁液を室温で激しく攪拌している中に、30%過酸化水素水(14.1 g、0.111 mol)を滴下して加えた後、室温で0.5時間激しく攪拌した。2-ブトキシ-7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)エチルナフタレン(15.6 g、0.037 mol)のテトラヒドロフラン(75 ml)溶液を加えた後、室温で24時間激しく攪拌した。反応液を濾過してホウ酸を濾別した後、少量のテトラヒドロフランでホウ酸を洗滌し、有機層を合わせた後、5%炭酸水素ナトリウム水溶液、飽和食塩水の順で洗條し、無水硫酸ナトリウムで乾燥した。塩を濾別後、溶媒を留去し、褐色の固体を得た。得られた固体をカラム(シリカゲル、トルエン)により精製することにより、薄黄色の固体(10.5 g)を得た。(収率 70.1%)
（実施例1-5）7-ブトキシ-1,2-ジフルオロ-3-[2-(トランス-4-プロピルシクロヘキシル)エチル]-8-(トリフルオロメトキシ)ナフタレン(I-1)
(以下、ドラフト中で行う。) 2-ブトキシ-7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)エチル-1-ナフトール(10.5 g、0.026 mol)の無水N,N-ジメチルホルムアミド(110 ml)懸濁液を激しく攪拌している中に、1-(トリフルオロメチル)-1,2-ベンズヨードキソール-3-(1H)-オン(32.9 g、0.104 mol)を加えた。90℃で24時間加熱攪拌した後、反応液を放冷し、水に空けて反応を終了させた。水層から酢酸エチルで抽出し、有機層を集めた後、10%チオ硫酸ナトリウム水溶液、飽和炭酸水素ナトリウム水溶液、飽和食塩水の順で洗條し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、得られた橙色の固体をカラム(シリカゲル／ヘキサン、ジクロロメタン)を用いて精製し、再結晶(エタノール、メタノール)することにより、無色の針状晶(3.9 g)を得た。(収率 31.7%)
1H-NMR (400MHz, CDCl3) σ(ppm) 0.87 (t, 3H), 0.99 (t, 3H), 0.82-1.88 (m, 20H), 2.69 (t, 2H), 4.10 (t, 2H), 6.60-7.20 (m, 3H)
MS m/z 472(M+)
相転移温度(℃) Cr 55 Iso
（実施例２）7-ブトキシ-1,2-ジフルオロ-3-[2-(トランス-4-プロピルシクロヘキシル)メトキシ]-8-(トリフルオロメトキシ)ナフタレン(I-2)の合成
Example 1-1 7,8-Difluoro-6- (trans-4-propylcyclohexyl) ethyl-2-naphthol
(The following is carried out in a fume hood) 7-butoxy-1,2-difluoro-3- (trans-4-propylcyclohexyl) ethylnaphthalene (22.0 g, 0.056 mol) in a dichloromethane (220 ml) solution in 1.0 M Boron tribromide dichloromethane solution (86 ml, 0.086 mol) was added, followed by stirring at room temperature for 24 hours. Water was added dropwise, and the mixture was stirred at room temperature for 0.5 hour. The organic layer was separated and extracted from the aqueous layer with dichloromethane. The organic layers were combined, washed with 5% aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate. After the salt was filtered off, the solvent was distilled off to obtain a pale yellow solid (19.0 g). (Yield quantitative)
Example 1-2 7,8-difluoro-1-formyl-6- (trans-4-propylcyclohexyl) ethyl-2-naphthol
(The following is carried out in a draft.) A solution of 7,8-difluoro-6- (trans-4-propylcyclohexyl) ethyl-2-naphthol (19.0 g, 0.057 mol) in dichloromethane (475 ml) was brought to 5-10 ° C. While stirring vigorously while cooling, dichloromethyl methyl ether (14.5 ml, 0.164 mol) was added, and then titanium (IV) chloride (24 ml, A solution of 0.219 mol) in dichloromethane (50 ml) was added dropwise over 0.5 hours, and the mixture was stirred for 1 hour while maintaining the internal temperature at 5 to 10 ° C. The reaction solution was added dropwise to ice water to stop the reaction, and then stirred at room temperature for 0.5 hour. The organic layer was separated and extracted from the aqueous layer with dichloromethane. The organic layers were combined, washed with 5% aqueous sodium hydrogen carbonate solution and saturated brine in that order, and dried over anhydrous sodium sulfate. After the salt was filtered off, the solvent was distilled off to obtain a brown solid. The obtained solid was recrystallized (dichloromethane, methanol) to obtain a red pink powder (15.2 g). (Yield 73.0%)
Example 1-3 2-Butoxy-7,8-difluoro-1-formyl-6- (trans-4-propylcyclohexyl) ethylnaphthalene
(The following is performed in a nitrogen atmosphere.) 7,8-Difluoro-1-formyl-6- (trans-4-propylcyclohexyl) ethyl-2-naphthol (18.6 g, 0.051 mol) and anhydrous potassium carbonate (14.1 g, 0.102 mol) of N, N-dimethylformamide (DMF, 200 ml) suspension was vigorously stirred at room temperature for 0.5 hour. After adding 1-bromobutane (9.0 g, 0.066 mol), the mixture was heated to reflux for 6 hours and allowed to cool to room temperature. The reaction solution was added to water to stop the reaction, and the precipitated solid was dissolved in toluene. The organic layer was separated and the aqueous layer was extracted with toluene. The organic layers were combined, washed with saturated brine, passed through the column (silica gel) as it was, and further washed with toluene. After the organic layers were combined, the solvent was distilled off to obtain a brown liquid. The obtained liquid was distilled under reduced pressure to obtain a pale yellow liquid. The obtained liquid was recrystallized (ethyl acetate, methanol) to obtain a light red solid (18.6 g). (Yield 86.1%)
(Example 1-4) 2-butoxy-7,8-difluoro-6- (trans-4-propylcyclohexyl) ethyl-1-naphthol
(The following is carried out in a draft.) While a suspension of boric acid (12.7 g, 0.205 mol) in tetrahydrofuran (180 ml) was vigorously stirred at room temperature, 30% aqueous hydrogen peroxide (14.1 g, 0.111 mol) ) Was added dropwise, followed by vigorous stirring at room temperature for 0.5 hour. After adding a solution of 2-butoxy-7,8-difluoro-1-formyl-6- (trans-4-propylcyclohexyl) ethylnaphthalene (15.6 g, 0.037 mol) in tetrahydrofuran (75 ml), vigorously at room temperature for 24 hours. Stir. After filtering the reaction solution to remove boric acid, the boric acid was washed with a small amount of tetrahydrofuran, and the organic layers were combined, then washed with 5% aqueous sodium hydrogen carbonate solution and saturated brine in that order, and anhydrous sulfuric acid. Dry with sodium. After the salt was filtered off, the solvent was distilled off to obtain a brown solid. The obtained solid was purified by a column (silica gel, toluene) to obtain a pale yellow solid (10.5 g). (Yield 70.1%)
Example 1-5 7-butoxy-1,2-difluoro-3- [2- (trans-4-propylcyclohexyl) ethyl] -8- (trifluoromethoxy) naphthalene (I-1)
(The following is carried out in a draft.) 2-Butoxy-7,8-difluoro-6- (trans-4-propylcyclohexyl) ethyl-1-naphthol (10.5 g, 0.026 mol) in anhydrous N, N-dimethylformamide ( 110 ml) While the suspension was vigorously stirred, 1- (trifluoromethyl) -1,2-benziodoxol-3- (1H) -one (32.9 g, 0.104 mol) was added. After stirring with heating at 90 ° C. for 24 hours, the reaction solution was allowed to cool and poured into water to complete the reaction. The aqueous layer was extracted with ethyl acetate, and the organic layer was collected. The organic layer was washed with a 10% aqueous sodium thiosulfate solution, a saturated aqueous sodium bicarbonate solution, and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the resulting orange solid was purified using a column (silica gel / hexane, dichloromethane) and recrystallized (ethanol, methanol) to give colorless needle crystals (3.9 g). . (Yield 31.7%)
1H-NMR (400MHz, CDCl3) σ (ppm) 0.87 (t, 3H), 0.99 (t, 3H), 0.82-1.88 (m, 20H), 2.69 (t, 2H), 4.10 (t, 2H), 6.60 -7.20 (m, 3H)
MS m / z 472 (M + )
Phase transition temperature (℃) Cr 55 Iso
Example 2 Synthesis of 7-butoxy-1,2-difluoro-3- [2- (trans-4-propylcyclohexyl) methoxy] -8- (trifluoromethoxy) naphthalene (I-2)
（実施例2-1）7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)メトキシ-2-ナフトール
(以下、オートクレーブ中で行う。) 7-ベンジルオキシ-1,2-ジフルオロ-3-(トランス-4-プロピルシクロヘキシル)メトキシナフタレン(25.0 g、0.059 mol)のトルエン(175 ml)、エタノール(75 ml)混合溶液中に、5%パラジウム炭素(1.2 g)を加えた後、水素圧(0.2 MPa)下、室温で4時間攪拌した。触媒を濾別後、溶媒を留去し、薄黄色の固体(19.6 g)を得た。(収率 定量的)
（実施例2-2）7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)メトキシ-2-ナフトール
実施例1-2の7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)エチル-2-ナフトールに代えて、7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)メトキシ-2-ナフトールを用いることにより、7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)メトキシ-2-ナフトールを得た。
Example 2-1 7,8-difluoro-6- (trans-4-propylcyclohexyl) methoxy-2-naphthol
(The following is carried out in an autoclave.) 7-Benzyloxy-1,2-difluoro-3- (trans-4-propylcyclohexyl) methoxynaphthalene (25.0 g, 0.059 mol) in toluene (175 ml), ethanol (75 ml ) After 5% palladium carbon (1.2 g) was added to the mixed solution, the mixture was stirred at room temperature for 4 hours under hydrogen pressure (0.2 MPa). After the catalyst was filtered off, the solvent was distilled off to obtain a pale yellow solid (19.6 g). (Yield quantitative)
Example 2-2 7,8-difluoro-1-formyl-6- (trans-4-propylcyclohexyl) methoxy-2-naphthol Example 7,7-8-difluoro-6- (trans-4 By using 7,8-difluoro-6- (trans-4-propylcyclohexyl) methoxy-2-naphthol instead of -propylcyclohexyl) ethyl-2-naphthol, 7,8-difluoro-1-formyl-6 -(Trans-4-propylcyclohexyl) methoxy-2-naphthol was obtained.
（実施例2-3）2-ブトキシ-7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)メトキシナフタレン
実施例1-3の7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)エチル-2-ナフトールに代えて、7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)メトキシ-2-ナフトールを用いることにより、2-ブトキシ-7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)メトキシナフタレンを得た。
Example 2-3 2-butoxy-7,8-difluoro-1-formyl-6- (trans-4-propylcyclohexyl) methoxynaphthalene 7,8-difluoro-1-formyl-6 of Example 1-3 By using 7,8-difluoro-1-formyl-6- (trans-4-propylcyclohexyl) methoxy-2-naphthol instead of-(trans-4-propylcyclohexyl) ethyl-2-naphthol, Butoxy-7,8-difluoro-1-formyl-6- (trans-4-propylcyclohexyl) methoxynaphthalene was obtained.
（実施例2-4）2-ブトキシ-7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)メトキシ-1-ナフトール
実施例1-4の2-ブトキシ-7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)エチルナフタレンに代えて、2-ブトキシ-7,8-ジフルオロ-1-ホルミル-6-(トランス-4-プロピルシクロヘキシル)メトキシナフタレンを用いることにより、2-ブトキシ-7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)メトキシ-1-ナフトールを得た。
Example 2-4 2-butoxy-7,8-difluoro-6- (trans-4-propylcyclohexyl) methoxy-1-naphthol 2-butoxy-7,8-difluoro-1- of Example 1-4 By using 2-butoxy-7,8-difluoro-1-formyl-6- (trans-4-propylcyclohexyl) methoxynaphthalene instead of formyl-6- (trans-4-propylcyclohexyl) ethylnaphthalene, 2 -Butoxy-7,8-difluoro-6- (trans-4-propylcyclohexyl) methoxy-1-naphthol was obtained.
（実施例2-5）7-ブトキシ-1,2-ジフルオロ-3-[2-(トランス-4-プロピルシクロヘキシル)メトキシ]-8-(トリフルオロメトキシ)ナフタレン(I-2)
実施例1-5の2-ブトキシ-7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)エチル-1-ナフトールに代えて、2-ブトキシ-7,8-ジフルオロ-6-(トランス-4-プロピルシクロヘキシル)メトキシ-1-ナフトールを用いることにより、7-ブトキシ-1,2-ジフルオロ-3-[2-(トランス-4-プロピルシクロヘキシル)メトキシ]-8-(トリフルオロメトキシ)ナフタレンを得た。
1H-NMR (400MHz, CDCl3) σ(ppm) 0.87 (t, 3H), 0.96 (t, 3H), 0.82-1.88 (m, 18H), 3.96 (t, 2H), 4.10 (t, 2H), 6.60-7.22 (m, 3H)
MS m/z 474(M+)
相転移温度(℃) Cr 90 I
(実施例３) 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)
Example 2-5 7-butoxy-1,2-difluoro-3- [2- (trans-4-propylcyclohexyl) methoxy] -8- (trifluoromethoxy) naphthalene (I-2)
Instead of 2-butoxy-7,8-difluoro-6- (trans-4-propylcyclohexyl) ethyl-1-naphthol in Example 1-5, 2-butoxy-7,8-difluoro-6- (trans- By using 4-propylcyclohexyl) methoxy-1-naphthol, 7-butoxy-1,2-difluoro-3- [2- (trans-4-propylcyclohexyl) methoxy] -8- (trifluoromethoxy) naphthalene is obtained. Obtained.
1H-NMR (400MHz, CDCl3) σ (ppm) 0.87 (t, 3H), 0.96 (t, 3H), 0.82-1.88 (m, 18H), 3.96 (t, 2H), 4.10 (t, 2H), 6.60 -7.22 (m, 3H)
MS m / z 474 (M + )
Phase transition temperature (℃) Cr 90 I
(Example 3) Preparation of liquid crystal composition (1)
Host liquid crystal composition comprising the following composition (H)
を調製した。ここで(H)の物性値は以下の通りである。 Was prepared. Here, the physical properties of (H) are as follows.
ネマチック相上限温度(TN-I)： 103.2℃
誘電率異方性(Δε)： 0.03
屈折率異方性(Δn)： 0.099
このホスト液晶(H)80％と実施例1で得られた(I-1)
Nematic phase upper limit temperature (T NI ): 103.2 ℃
Dielectric anisotropy (Δε): 0.03
Refractive index anisotropy (Δn): 0.099
This host liquid crystal (H) 80% and obtained in Example 1 (I-1)
20％からなる液晶組成物(M-1)を調製した。この組成物の物性値は以下の通りである。 A liquid crystal composition (M-1) comprising 20% was prepared. The physical properties of this composition are as follows.
ネマチック相上限温度(TN-I)： 93.1℃
誘電率異方性(Δε)： −1.73
屈折率異方性(Δn)： 0.106
本発明の化合物(I-1)を含有する液晶組成物(M-1)は、母体液晶(H)に比べ、誘電率異方性(Δε)は大きく減少して負の値となった。このことから、本発明の化合物(I-1)は、誘電率異方性が負であり、その絶対値が極めて大きいことがわかる。
Nematic phase upper limit temperature (T NI ): 93.1 ℃
Dielectric anisotropy (Δε): −1.73
Refractive index anisotropy (Δn): 0.106
In the liquid crystal composition (M-1) containing the compound (I-1) of the present invention, the dielectric anisotropy (Δε) was greatly reduced to a negative value as compared with the base liquid crystal (H). This shows that the compound (I-1) of the present invention has a negative dielectric anisotropy and an extremely large absolute value.
また、(M-1)の電圧保持率を80℃で測定したところ、ホスト液晶組成物(H)の電圧保持率に対して98%以上と高い値を示した。このことから本発明の化合物(I-1)は安定性の面からも液晶表示材料として十分使用可能であることがわかる。 Further, when the voltage holding ratio of (M-1) was measured at 80 ° C., it showed a high value of 98% or more with respect to the voltage holding ratio of the host liquid crystal composition (H). This shows that the compound (I-1) of the present invention can be sufficiently used as a liquid crystal display material from the viewpoint of stability.
(比較例１) 液晶組成物の調製(2)
実施例1で調製したホスト液晶(H)80%に化合物(I-1)と比較的類似の構造を有するが、トリフルオロメトキシ基をフッ素原子に替えた化合物(J-1)
(Comparative Example 1) Preparation of liquid crystal composition (2)
Compound (J-1) wherein 80% of the host liquid crystal (H) prepared in Example 1 has a structure relatively similar to that of Compound (I-1), but the trifluoromethoxy group is replaced with a fluorine atom
20％からなる液晶組成物(M-2)を調製した。この組成物の物性値は以下の通りである。 A liquid crystal composition (M-2) comprising 20% was prepared. The physical properties of this composition are as follows.
ネマチック相上限温度(TN-I)： 95.4℃
誘電率異方性(Δε)： −1.33
屈折率異方性(Δn)： 0.106
化合物(J-1)を含有する液晶組成物(M-2)は、実施例1記載の(M-1)と比べ、誘電率異方性の絶対値が小さいことがわかる。
Nematic phase upper limit temperature (T NI ): 95.4 ℃
Dielectric anisotropy (Δε): −1.33
Refractive index anisotropy (Δn): 0.106
It can be seen that the liquid crystal composition (M-2) containing the compound (J-1) has a smaller absolute value of dielectric anisotropy than (M-1) described in Example 1.
(実施例４) 液晶組成物の調製(3)
実施例３で調製したホスト液晶(H)90%に化合物(I-2)
(Example 4) Preparation of liquid crystal composition (3)
Compound (I-2) was added to 90% of the host liquid crystal (H) prepared in Example 3.
10％からなる液晶組成物(M-3)を調製した。この組成物の物性値は以下の通りである。 A liquid crystal composition (M-3) comprising 10% was prepared. The physical properties of this composition are as follows.
ネマチック相上限温度(TN-I)： 98.9℃
誘電率異方性(Δε)： −1.08
屈折率異方性(Δn)： 0.102
本発明の化合物(I-2)を含有する液晶組成物(M-3)は、母体液晶(H)に比べ、誘電率異方性(Δε)は大きく減少して負の値となった。このことから、本発明の化合物は(I-2)は、誘電率異方性が負であり、その絶対値が極めて大きいことがわかる。
Nematic phase upper limit temperature (T NI ): 98.9 ℃
Dielectric anisotropy (Δε): −1.08
Refractive index anisotropy (Δn): 0.102
In the liquid crystal composition (M-3) containing the compound (I-2) of the present invention, the dielectric anisotropy (Δε) was greatly reduced to a negative value as compared with the base liquid crystal (H). From this, it can be seen that the compound of the present invention (I-2) has a negative dielectric anisotropy and an extremely large absolute value.
また、(M-3)の電圧保持率を80℃で測定したところ、ホスト液晶組成物(H)の電圧保持率に対して98%以上と高い値を示した。このことから本発明の化合物(I-2)は安定性の面からも液晶表示材料として十分使用可能であることがわかる。 Further, when the voltage holding ratio of (M-3) was measured at 80 ° C., it showed a high value of 98% or more with respect to the voltage holding ratio of the host liquid crystal composition (H). This shows that the compound (I-2) of the present invention can be sufficiently used as a liquid crystal display material from the viewpoint of stability.
(実施例５) 液晶組成物の調製(4)
以下の組成からなる液晶組成物(M-4)を調製した。
(Example 5) Preparation of liquid crystal composition (4)
A liquid crystal composition (M-4) having the following composition was prepared.
この(M-3)の物性値は以下の通りであった。 The physical properties of (M-3) were as follows.
ネマチック相上限温度(TN-I)： 98.8℃
誘電率異方性(Δε)： −4.00
屈折率異方性(Δn)： 0.100
ここで作製した組成物を用いて、電圧保持率を測定したところ80℃で98%と高い値を示し、優れた表示特性を示す液晶表示装置を作成することができた。
Nematic phase upper limit temperature (T NI ): 98.8 ℃
Dielectric anisotropy (Δε): −4.00
Refractive index anisotropy (Δn): 0.100
When the voltage holding ratio was measured using the composition prepared here, it was as high as 98% at 80 ° C., and a liquid crystal display device having excellent display characteristics could be produced.
(実施例６) 液晶組成物の調製(5)
以下の組成からなる液晶組成物(M-5)を調製した。
(Example 6) Preparation of liquid crystal composition (5)
A liquid crystal composition (M-5) having the following composition was prepared.
この(M-5)の物性値は以下の通りであった。 The physical properties of (M-5) were as follows.
ネマチック相上限温度(TN-I)： 93.4℃
誘電率異方性(Δε)： −3.37
屈折率異方性(Δn)： 0.090
ここで作製した組成物を用いて、電圧保持率を測定したところ80℃で98%と高い値を示し、優れた表示特性を示す液晶表示装置を作成することができた。
Nematic phase upper limit temperature (T NI ): 93.4 ℃
Dielectric anisotropy (Δε): −3.37
Refractive index anisotropy (Δn): 0.090
When the voltage holding ratio was measured using the composition prepared here, it was as high as 98% at 80 ° C., and a liquid crystal display device having excellent display characteristics could be produced.
Claims (10)
Ａ１、Ａ２、Ｂ１およびＢ２は、それぞれ独立的にトランス−１，４−シクロヘキシレン基、トランス−１，３−ジオキサン−２，５−ジイル基、ピリジン−２，５−ジイル基、ピリミジン−２，５−ジイル基または１個以上の水素原子がフッ素原子に置換されていてもよい１，４−フェニレン基を表し、
Ｌ１、Ｌ２、Ｍ１およびＭ２は、それぞれ独立的に単結合、−ＣＨ２ＣＨ２−、−ＣＨ＝ＣＨ−、−ＣＨ≡ＣＨ−、−ＯＣＨ２−、−ＣＨ２Ｏ−、−ＯＣＦ２−、−ＣＦ２Ｏ−、−ＣＦ２ＣＦ２−、−ＣＦ＝ＣＦ−、−ＯＣＯ−、−ＣＯＯ−、−ＣＨ（ＣＨ３）ＣＨ２−、−ＣＨ２ＣＨ（ＣＨ３）−、−ＣＨ（ＣＨ３）ＣＨ（ＣＨ３）−、−ＯＣＨ（ＣＨ３）−、−ＣＨ（ＣＨ３）Ｏ−、−（ＣＨ２）４−、−（ＣＨ２）３Ｏ−、−Ｏ（ＣＨ２）３−、−ＣＯＳ−または−ＳＣＯ−を表し、
Ｘ １ はフッ素原子を表し、Ｘ ２はそれぞれ独立的に水素原子またはフッ素原子を表し、
ｐ、ｑ、ｒおよびｓは、それぞれ独立的に０または１を表す。）で表される１−（トリフルオロメトキシ）ナフタレン誘導体。 Formula (I)
A 1 , A 2 , B 1 and B 2 are each independently a trans-1,4-cyclohexylene group, a trans-1,3-dioxane-2,5-diyl group, or a pyridine-2,5-diyl group. , A pyrimidine-2,5-diyl group or a 1,4-phenylene group in which one or more hydrogen atoms may be substituted with fluorine atoms,
L 1 , L 2 , M 1 and M 2 are each independently a single bond, —CH 2 CH 2 —, —CH═CH—, —CH≡CH—, —OCH 2 —, —CH 2 O—, -OCF 2 -, - CF 2 O -, - CF 2 CF 2 -, - CF = CF -, - OCO -, - COO -, - CH (CH 3) CH 2 -, - CH 2 CH (CH 3) -, - CH (CH 3) CH (CH 3) -, - OCH (CH 3) -, - CH (CH 3) O -, - (CH 2) 4 -, - (CH 2) 3 O -, - Represents O (CH 2 ) 3 —, —COS— or —SCO—,
X 1 represents a fluorine atom, X 2 each independently represents a hydrogen atom or a fluorine atom,
p, q, r and s each independently represent 0 or 1; 1- (trifluoromethoxy) naphthalene derivative represented by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008180081A JP5382406B2 (en) | 2008-07-10 | 2008-07-10 | 1- (Trifluoromethoxy) naphthalene derivative |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2008180081A JP5382406B2 (en) | 2008-07-10 | 2008-07-10 | 1- (Trifluoromethoxy) naphthalene derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2010018542A JP2010018542A (en) | 2010-01-28 |
| JP5382406B2 true JP5382406B2 (en) | 2014-01-08 |
Family
ID=41703808
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008180081A Expired - Fee Related JP5382406B2 (en) | 2008-07-10 | 2008-07-10 | 1- (Trifluoromethoxy) naphthalene derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5382406B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5382405B2 (en) * | 2008-07-10 | 2014-01-08 | Ｄｉｃ株式会社 | 1- (Trifluoromethoxy) naphthalene derivative |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4487327B2 (en) * | 1998-12-08 | 2010-06-23 | Ｄｉｃ株式会社 | NOVEL LIQUID CRYSTALLINE COMPOUND, LIQUID CRYSTALLINE COMPOSITION COMPRISING SAME, AND PROCESS FOR PRODUCING THE SAME |
| JP4461497B2 (en) * | 1998-10-16 | 2010-05-12 | Ｄｉｃ株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
| JP4691746B2 (en) * | 1999-07-28 | 2011-06-01 | Ｄｉｃ株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
| JP4655479B2 (en) * | 2004-01-28 | 2011-03-23 | Ｄｉｃ株式会社 | Nematic liquid crystal composition and liquid crystal display device using the same |
| JP5382405B2 (en) * | 2008-07-10 | 2014-01-08 | Ｄｉｃ株式会社 | 1- (Trifluoromethoxy) naphthalene derivative |
-
2008
- 2008-07-10 JP JP2008180081A patent/JP5382406B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010018542A (en) | 2010-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TW201139354A (en) | Liquid-crystalline compounds and liquid-crystalline media | |
| JP4044617B2 (en) | Liquid crystalline compound having negative dielectric anisotropy value, liquid crystal composition, and liquid crystal display device | |
| CN107207965B (en) | Nematic liquid crystal composition and liquid crystal display element using same | |
| JP5062472B2 (en) | 1- (trifluoromethyl) naphthalene derivative | |
| JP4228323B2 (en) | 1- (trifluoromethyl) naphthalene derivative | |
| JP5604809B2 (en) | Fluorobenzene derivative and liquid crystal composition containing the compound | |
| JP4691893B2 (en) | Liquid crystal composition, display element and compound containing trifluoronaphthalene derivative. | |
| TWI588243B (en) | Compounds having a fluorinated naphthalene structure and liquid crystal | |
| JP5614003B2 (en) | Difluorobenzene derivative, liquid crystal composition containing the compound, and liquid crystal display device | |
| JP4876420B2 (en) | Difluorobenzene derivative | |
| JP5493596B2 (en) | Difluorobenzene derivatives and liquid crystal compositions containing the same. | |
| JP5526686B2 (en) | Difluorobenzene derivatives and liquid crystal compositions containing the same. | |
| CN110650948A (en) | Liquid crystal compound and composition thereof | |
| JP5382406B2 (en) | 1- (Trifluoromethoxy) naphthalene derivative | |
| CN112457865B (en) | Liquid crystal compound and composition and application thereof | |
| JP5382405B2 (en) | 1- (Trifluoromethoxy) naphthalene derivative | |
| CN109181712A (en) | A kind of benzofuran liquid-crystal compounds and combinations thereof with difluoromethyl ether bridged bond | |
| JP4759949B2 (en) | 2-naphthyl-1,3-dioxane derivatives | |
| CN112500867B (en) | Liquid crystal compound, liquid crystal composition composed of same and application | |
| JP4835032B2 (en) | Trifluoronaphthalene derivative | |
| CN102603472B (en) | Lateral-difluoro-containing liquid crystal compounds, and preparation method and application thereof | |
| JP4936104B2 (en) | Trifluoronaphthalene derivative and liquid crystal composition containing the compound | |
| JP4779493B2 (en) | 2-naphthyl-1,3-dioxane derivatives | |
| JP4753064B2 (en) | Liquid crystal composition, display element and compound containing trifluoronaphthalene derivative. | |
| JP4978770B2 (en) | Trifluoronaphthalene derivative and liquid crystal composition containing the compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20110511 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A132 Effective date: 20130618 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20130620 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130809 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130905 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130918 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5382406 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |