JP3900554B2 - Liquid crystalline compounds with extremely large dielectric anisotropy - Google Patents
Liquid crystalline compounds with extremely large dielectric anisotropy Download PDFInfo
- Publication number
- JP3900554B2 JP3900554B2 JP20470896A JP20470896A JP3900554B2 JP 3900554 B2 JP3900554 B2 JP 3900554B2 JP 20470896 A JP20470896 A JP 20470896A JP 20470896 A JP20470896 A JP 20470896A JP 3900554 B2 JP3900554 B2 JP 3900554B2
- Authority
- JP
- Japan
- Prior art keywords
- ethynyl
- propyl
- difluorophenyl
- difluorobenzene
- difluoro
- 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 - Lifetime
Links
- 150000001875 compounds Chemical class 0.000 title claims description 51
- 239000007788 liquid Substances 0.000 title description 7
- 239000004973 liquid crystal related substance Substances 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 27
- 125000001153 fluoro group Chemical group F* 0.000 claims description 16
- 229910052731 fluorine Inorganic materials 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- 125000000876 trifluoromethoxy group Chemical group FC(F)(F)O* 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004786 difluoromethoxy group Chemical group [H]C(F)(F)O* 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 2
- -1 4-substituted cyclohexanecarboxylic Chemical class 0.000 description 78
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 16
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011630 iodine Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- XCFAMIFCPFIXGL-UHFFFAOYSA-N 1,3-difluoro-2-iodo-5-propylbenzene Chemical compound CCCC1=CC(F)=C(I)C(F)=C1 XCFAMIFCPFIXGL-UHFFFAOYSA-N 0.000 description 4
- HVCALSKQNAOZOG-UHFFFAOYSA-N 2-[2-(3,5-difluoro-4-iodophenyl)ethynyl]-1,3-difluoro-5-propylbenzene Chemical compound FC1=CC(CCC)=CC(F)=C1C#CC1=CC(F)=C(I)C(F)=C1 HVCALSKQNAOZOG-UHFFFAOYSA-N 0.000 description 4
- JMRYYPXLXRFUEK-UHFFFAOYSA-N 2-[2-(3,5-difluorophenyl)ethynyl]-1,3-difluoro-5-propylbenzene Chemical compound FC1=CC(CCC)=CC(F)=C1C#CC1=CC(F)=CC(F)=C1 JMRYYPXLXRFUEK-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical class C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ANCGPYMWZXRYBC-UHFFFAOYSA-N C(CC)C1=CC(=C(C(=C1)F)C1=C(C(=C(C(=C1)F)C#CC1=CC(=C(C(=C1)F)F)F)F)C#C)F Chemical compound C(CC)C1=CC(=C(C(=C1)F)C1=C(C(=C(C(=C1)F)C#CC1=CC(=C(C(=C1)F)F)F)F)C#C)F ANCGPYMWZXRYBC-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 238000006138 lithiation reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 0 *C(CC1)CCC1c1cc(F)c(CCc(cc2F)cc(F)c2F)c(F)c1 Chemical compound *C(CC1)CCC1c1cc(F)c(CCc(cc2F)cc(F)c2F)c(F)c1 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- OAYXLFQUJBXCMH-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC)F)F)F OAYXLFQUJBXCMH-UHFFFAOYSA-N 0.000 description 2
- IXSSDJIWOMSCLY-UHFFFAOYSA-N CCCC1=CC(=C(C=C1)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)C(F)(F)F)F)F)F Chemical compound CCCC1=CC(=C(C=C1)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)C(F)(F)F)F)F)F IXSSDJIWOMSCLY-UHFFFAOYSA-N 0.000 description 2
- LJAVRFRTKYXFIQ-UHFFFAOYSA-N CCCC1=CC(=C(C=C1)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC(F)(F)F)F)F)F Chemical compound CCCC1=CC(=C(C=C1)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC(F)(F)F)F)F)F LJAVRFRTKYXFIQ-UHFFFAOYSA-N 0.000 description 2
- LRKYZEXKHXUBMY-UHFFFAOYSA-N CCCC1=CC(=C(C=C1)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC(F)F)F)F)F Chemical compound CCCC1=CC(=C(C=C1)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC(F)F)F)F)F LRKYZEXKHXUBMY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 239000012769 display material Substances 0.000 description 2
- 230000026045 iodination Effects 0.000 description 2
- 238000006192 iodination reaction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical class C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- AXTNQJKYTXEYRM-UHFFFAOYSA-N 1,3-difluoro-5-propylbenzene Chemical compound CCCC1=CC(F)=CC(F)=C1 AXTNQJKYTXEYRM-UHFFFAOYSA-N 0.000 description 1
- OTDGZDMGSFBZLI-UHFFFAOYSA-N 1-ethynyl-3,5-difluorobenzene Chemical compound FC1=CC(F)=CC(C#C)=C1 OTDGZDMGSFBZLI-UHFFFAOYSA-N 0.000 description 1
- BZXWRVPVZZZAKB-UHFFFAOYSA-N 5-ethynyl-1,2,3-trifluorobenzene Chemical compound FC1=CC(C#C)=CC(F)=C1F BZXWRVPVZZZAKB-UHFFFAOYSA-N 0.000 description 1
- PBJGXMKIHIANAB-UHFFFAOYSA-N CCC(C(CC1)CCC1c(cc1F)cc(F)c1C#Cc(cc1F)cc(F)c1F)(N)I Chemical compound CCC(C(CC1)CCC1c(cc1F)cc(F)c1C#Cc(cc1F)cc(F)c1F)(N)I PBJGXMKIHIANAB-UHFFFAOYSA-N 0.000 description 1
- QNCPUOQRTCHGQY-UHFFFAOYSA-N CCC(c(cc1C2CC2)cc(F)c1C#Cc(cc1F)cc(F)c1I)(N)I Chemical compound CCC(c(cc1C2CC2)cc(F)c1C#Cc(cc1F)cc(F)c1I)(N)I QNCPUOQRTCHGQY-UHFFFAOYSA-N 0.000 description 1
- BJGSMKMCESBGTI-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=C(C(=C(C=C2)C#CC3=CC(=C(C(=C3)F)OC(F)F)F)F)C#C)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=C(C(=C(C=C2)C#CC3=CC(=C(C(=C3)F)OC(F)F)F)F)C#C)F BJGSMKMCESBGTI-UHFFFAOYSA-N 0.000 description 1
- FKSRFPWKGTWWRG-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=C(C(=C(C=C2)C#CC3=CC(=C(C=C3)OC(F)(F)F)F)F)C#C)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=C(C(=C(C=C2)C#CC3=CC(=C(C=C3)OC(F)(F)F)F)F)C#C)F FKSRFPWKGTWWRG-UHFFFAOYSA-N 0.000 description 1
- HVRFQBFJXGKOFN-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=C(C(=C(C=C2)C#CC3=CC(=C(C=C3)OC)F)F)C#C)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=C(C(=C(C=C2)C#CC3=CC(=C(C=C3)OC)F)F)C#C)F HVRFQBFJXGKOFN-UHFFFAOYSA-N 0.000 description 1
- SCRIJHLOUYHUPK-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)C#N)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)C#N)F)F)F SCRIJHLOUYHUPK-UHFFFAOYSA-N 0.000 description 1
- WBXQTVFKYBHFQU-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)C)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)C)F)F)F WBXQTVFKYBHFQU-UHFFFAOYSA-N 0.000 description 1
- UBYTVOVDUGSUJU-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)CC)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)CC)F)F)F UBYTVOVDUGSUJU-UHFFFAOYSA-N 0.000 description 1
- GSUJFSAPISHBJB-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)CCC)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)CCC)F)F)F GSUJFSAPISHBJB-UHFFFAOYSA-N 0.000 description 1
- RBFCNWAIIHBHSY-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC(F)(F)F)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC(F)(F)F)F)F)F RBFCNWAIIHBHSY-UHFFFAOYSA-N 0.000 description 1
- ZSNDGMSRMQVNAC-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC(F)F)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OC(F)F)F)F)F ZSNDGMSRMQVNAC-UHFFFAOYSA-N 0.000 description 1
- GXDRJGJBIJIGKT-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OCC)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OCC)F)F)F GXDRJGJBIJIGKT-UHFFFAOYSA-N 0.000 description 1
- FZXMQBOEOLHVIP-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OCCC)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)OCCC)F)F)F FZXMQBOEOLHVIP-UHFFFAOYSA-N 0.000 description 1
- UOSLYIFSIIWXDV-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C=C3)C(F)(F)F)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C=C3)C(F)(F)F)F)F)F UOSLYIFSIIWXDV-UHFFFAOYSA-N 0.000 description 1
- RWJHETXWJZPCBT-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C=C3)OC(F)(F)F)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C=C3)OC(F)(F)F)F)F)F RWJHETXWJZPCBT-UHFFFAOYSA-N 0.000 description 1
- XPUDTSCQWHQNEL-UHFFFAOYSA-N CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C=C3)OC(F)F)F)F)F Chemical compound CCCC1=CC(=C(C(=C1)F)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C=C3)OC(F)F)F)F)F XPUDTSCQWHQNEL-UHFFFAOYSA-N 0.000 description 1
- BEIBLHHKLKDUEM-UHFFFAOYSA-N CCCC1=CC(=C(C=C1)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)Cl)F)F)F Chemical compound CCCC1=CC(=C(C=C1)C2=CC(=C(C(=C2C#C)F)C#CC3=CC(=C(C(=C3)F)Cl)F)F)F BEIBLHHKLKDUEM-UHFFFAOYSA-N 0.000 description 1
- ZTBSEPKFTLQCER-UHFFFAOYSA-N CCCC1=CC(F)=C(C(C=C(C(C#CC2=CC(F)=C(C(F)(F)F)C(F)=C2)=C2F)F)=C2C#C)C(F)=C1 Chemical compound CCCC1=CC(F)=C(C(C=C(C(C#CC2=CC(F)=C(C(F)(F)F)C(F)=C2)=C2F)F)=C2C#C)C(F)=C1 ZTBSEPKFTLQCER-UHFFFAOYSA-N 0.000 description 1
- ACDCLWPKGXQJMR-UHFFFAOYSA-N CCCC1=CC(F)=C(C(C=CC(C#CC2=CC(F)=C(C(F)(F)F)C(F)=C2)=C2F)=C2C#C)C(F)=C1 Chemical compound CCCC1=CC(F)=C(C(C=CC(C#CC2=CC(F)=C(C(F)(F)F)C(F)=C2)=C2F)=C2C#C)C(F)=C1 ACDCLWPKGXQJMR-UHFFFAOYSA-N 0.000 description 1
- UAFAZPZMFRYENQ-UHFFFAOYSA-N CCCCC1=C(C=C(C=C1F)C#CC2=C(C=C(C(=C2F)C#C)C3=C(C=C(C=C3F)CCC)F)F)F Chemical compound CCCCC1=C(C=C(C=C1F)C#CC2=C(C=C(C(=C2F)C#C)C3=C(C=C(C=C3F)CCC)F)F)F UAFAZPZMFRYENQ-UHFFFAOYSA-N 0.000 description 1
- NVWYUCVVYIHYBH-UHFFFAOYSA-N CCCCCC1=C(C=C(C=C1F)C#CC2=C(C=C(C(=C2F)C#C)C3=C(C=C(C=C3F)CCC)F)F)F Chemical compound CCCCCC1=C(C=C(C=C1F)C#CC2=C(C=C(C(=C2F)C#C)C3=C(C=C(C=C3F)CCC)F)F)F NVWYUCVVYIHYBH-UHFFFAOYSA-N 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical class C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、電気光学的液晶表示材料として有用で新規な、誘電率異方性の極めて大きな液晶性化合物及びこの新規液晶性化合物を含有する液晶組成物に関する。
【０００２】
【従来の技術】
液晶表示素子は、時計、電卓をはじめとして、ワープロ、パーソナルコンピュータディスプレイ等、情報表示素子として用いられ、電子装置と人とのインターフェイスとして重要性を増している。
【０００３】
液晶を用いた表示方式は、電界効果（ＦＥＭ）型、動的散乱（ＤＳＭ）型及び熱効果（ＴＥＭ）型の３つに大別される。これらの効果を利用し種々の表示方式が提案されているが、現在までのところ、実用化されているのは電界効果型を用いた表示方式である。また、電界効果型には、ねじれネマチック（ＴＮ）型、超ねじれネマチック（ＳＴＮ）型、ゲスト-ホスト（ＧＨ）型、電界制御複屈折（ＥＣＢ）型、コレステリック-ネマチック相転移（ＣＮ-ＰＴ）型、表面安定化強誘電性液晶（ＳＳＦＬＣ）型等がある。この中で、現在主流となっているのはＴＮ型及びＳＴＮ型である。このうち、ＳＴＮ型では、駆動方式の改良等により、ある程度までは表示容量の増加は可能となったが、近年の大表示容量及び表示品位の要求にたいしては、もはや限界となった。そこで、表示画素ごとにしきい特性をもつ、２端子非線形素子を用いたＭＩＭ（Metal Insulator Metal）方式、３端子能動素子を用いたＴＦＴ（Thin Film Transistor）方式等のアクティブマトリックス方式が実用化され、大容量化に向けて急速に発展している。
【０００４】
これらの液晶表示方式に用いられている液晶材料には、各々の表示方式の特徴に応じて種々の特性が要求されているが、駆動電圧が低いことと応答が高速であることは、共通して特に重要な要求特性である。
【０００５】
駆動電圧を低くするためには、しきい値電圧を低下させる誘電率異方性（Δε）の大きな化合物が必要である。このΔεを大きくするためには、末端極性基に加えて、さらに多数のフッ素原子等の極性基を同一方向に導入する必要がある。
【０００６】
応答時間の短縮は、液晶組成物の粘度を低くすることにより可能であるが、素子のセル厚を薄くすることによっても達成できる。ただし、セル厚（ｄ）と屈折率異方性（Δｎ）の積(Δｎ・ｄ)は一定値に設定されているため、ｄを薄くするためには、Δｎの大きな液晶材料が必要である。また、強い白濁性を要求されるポリマー分散型液晶表示素子にも、Δｎの大きな化合物が必要とされる。
【０００７】
現在、Δｎが大きく且つΔεが大きい化合物としては、たとえばの式（ａ）のトラン誘導体が知られている。
【０００８】
【化２】
この式（ａ）の化合物は、Δｎ及びΔεが大きく、それを混合することにより組成物のΔｎを大きくさせ、しきい値電圧を低減させることができる。しかしながら、その程度は十分満足できるものではなかった。
【００１０】
従って、その混合により、さらに効果的にΔｎ及びΔεを大きくできる化合物が望まれていた。
【００１１】
【発明が解決しようとする課題】
本発明が解決しようとする課題は、大きなΔｎ及びΔεを有する新規液晶性化合物、及びこの液晶性化合物を用いることにより、Δｎが大きく、しきい値電圧の低い液晶組成物を提供することにある。
【００１２】
【課題を解決するための手段】
本発明は、上記課題を解決するために鋭意検討した結果、一般式（Ｉ）
【００１３】
【化３】
（式中、Ｒは炭素原子数１〜１０のアルキル基を表し、Ｙ1、Ｙ2、Ｙ3、Ｙ4、Ｙ5及びＹ6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、少なくとも４個はフッ素原子を表し、Ｚはフッ素原子、塩素原子、トリフルオロメトキシ基、ジフルオロメトキシ基、トリフルオロメチル基、シアノ基、炭素原子数１〜１０のアルキル基、アルコキシル基を表す。）で表される化合物及びこれを含有する液晶組成物を前記課題の解決手段として見出した。
【００１５】
【発明の実施の形態】
以下に本発明の液晶性化合物の一例について説明する。
一般式（Ｉ）において、ＺはΔεを大きく且つ汎用性をもたせるためにはフッ素原子、トリフルオロメトキシ基が好ましく、フッ素原子が特に好ましい。また、このときＲは炭素原子数１から７の直鎖状アルキル基が好ましく、炭素原子数２から５の直鎖状アルキル基がさらに好ましい。更に、Ｙ1、Ｙ2、Ｙ3、Ｙ4、Ｙ5及びＹ6においては５個以上がフッ素原子であることが好ましい。
【００１６】
本発明に係わる一般式（Ｉ）で表される化合物は、例えば、次のようにして製造することができる。
【００１７】
【化４】
（上記一般式（Ｉ）から（ＶＩＩ）の各式中で、Ｒ、Ｙ1、Ｙ2、Ｙ3、Ｙ4、Ｙ5、Ｙ6及びＺは一般式（Ｉ）におけると同じ意味を表し、Ｑ1、Ｑ2は臭素又はヨウ素原子を表す。）
第１工程：一般式（ＩＩ）の化合物を直接臭素又はヨウ素化する、もしくは、Ｙ5、Ｙ6がともにフッ素原子のときは、ｎ−ブチルリチウム等のリチオ化剤でリチオ化したのちに臭素又はヨウ素と反応させることにより一般式（ＩＩＩ）の化合物を製造する。
第２工程：一般式（ＩＩＩ）と一般式（ＩＶ）の化合物をパラジウム触媒と銅触媒の存在下で反応させることにより一般式（Ｖ）の化合物を製造する。
第３工程：一般式（Ｖ）の化合物を直接あるいは３重結合を保護した後に臭素又はヨウ素化する、もしくは、Ｙ3、Ｙ4がともにフッ素原子のときは、ｎ−ブチルリチウム等のリチオ化剤でリチオ化したのちに臭素又はヨウ素と反応させることにより一般式（ＶＩ）の化合物を製造する。あるいは第２工程において、一般式（ＩＶ）の化合物に換えて４位がアミノ基等で置換された化合物を用い、次いでその置換基を臭素またはヨウ素に変換してもよい。
第４工程：一般式（ＶＩ）と一般式（ＶＩＩ）の化合物をパラジウム触媒と銅触媒の存在下で反応させることにより本発明の一般式（Ｉ）の化合物を製造する。
【００１９】
斯くして製造された、一般式（Ｉ）で表される代表的な化合物を示す。
【００２０】
【化５】
融点：１７０．５℃
この本発明の一般式（Ｉ）で表される（Ｎｏ．１）の化合物５重量％及び現在汎用されているホスト液晶（Ａ）
【００２２】
【化６】
（式中、シクロヘキサン環はトランス配置である。）
９５重量％からなる液晶組成物（Ａ−１）を調製したところ、この組成物のΔｎは０．０９７であり、Δεは７．０であり、しきい値電圧は１．５０Ｖであった。ホスト液晶（Ａ）のΔｎは０．０９２であり、Δεは６．７であり、しきい値電圧は１．６０Ｖなので、わずかの添加にもかかわらず、Δｎ及びΔεを大きく増加させ、しきい値電圧を０．１Ｖも低下させることができた。
【００２４】
比較のために、先に示した式（ａ）の化合物５重量％及びホスト液晶（Ａ）９５重量％からなる比較組成物（Ａ−ａ）を調製した。同様に測定したところ、Δnは０．０９７と（Ａ−１）と同程度であったが、Δεは６．８までしか上昇せず、しきい値電圧は１．５５Ｖでありホスト液晶（Ａ）と比較して０．０５Ｖしか低下しなかった。
【００２５】
以上から本発明に係わる一般式（Ｉ）で表される化合物は、ホスト液晶に少量の添加で効果的にΔｎ及びΔεを大きくし、さらには、しきい値電圧を低下させることが可能であり、その効果は従来の化合物よりも優れていることが容易に理解することができる。
【００２６】
本発明はこのように、一般式（Ｉ）で表される化合物を含有する液晶組成物をも提供するものである。
さて、このように一般式（Ｉ）で表される化合物と混合することにより、液晶組成物と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、例えば、4-置換安息香酸-4-置換フェニル、4-置換シクロヘキサンカルボン酸-4-置換フェニル、4-置換シクロヘキサンカルボン酸-4-置換ビフェニル、4-(4-置換シクルヘキサンカルボニルオキシ)安息香酸-4-置換フェニル、4-(4-置換シクロヘキシル)安息香酸-4-置換フェニル、4-(4-置換シクロヘキシル)安息香酸-4-置換シクロヘキシル、4,4-置換ビフェニル、1-(4-置換フェニル)-4-置換シクロヘキサン、4,4-置換ターフェニル、1-(4-置換ビフェニリル)-4-置換シクロヘキサン、1-(4-置換シクロヘキシル)-4-(4-置換フェニル)シクロヘキサン、2-(4-置換フェニル)-5-置換ピリミジン、2-(4-置換ビフェニリル)-5-置換ピリミジン、1-(4-置換シクロヘキシル)-2-(4-置換シクロヘキシル)エタン、1-[4-(4-置換シクロヘキシル)シクロヘキシル]-2-(4-置換フェニル)エタン、1-[4-(4-置換フェニル)シクロヘキシル]-2-(4-置換シクロヘキシル)エタン、1-(4-置換フェニル)-2-(4-置換フェニル)エチン、1-[4-(4-置換シクロヘキシル)]-2-(4-置換フェニル)エチン及び上記の化合物でベンゼン環が側方フッ素置換された化合物等を挙げることができる。
【００２７】
【実施例】
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。
（実施例１） 4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,4,5-トリフルオロフェニル)エチニル-2,6-ジフルオロベンゼン（(No.1)の化合物）
（一般式（I）において、Ｒがプロピル基、Ｚ、Ｙ1、Ｙ2、Ｙ3、Ｙ4、Ｙ5及びＹ6がフッ素原子の化合物）の合成
（１） 4-プロピル-2,6-ジフルオロ-1-ヨードベンゼンの合成
【００２８】
【化７】
3,5-ジフルオロ-1-プロピルベンゼン30gをテトラヒドロフラン120mlに溶解し、-50℃に冷却した。攪拌下液温が-40℃を越えない速度でｎ−ブチルリチウムｎ−ヘキサン溶液(1.69mol/l)125mlを滴下し、さらに30分間攪拌した。ヨウ素53.7gのテトラヒドロフラン220ml溶液を液温が-40℃を越えない速度で滴下した。さらに30分間攪拌し、水10mlを加え室温にもどした。ヘキサン150mlを加え、10%亜硫酸水素ナトリウム水溶液、水、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、4-プロピル-2,6-ジフルオロ-1-ヨードベンゼン54.7gを得た。
（２） 1-(3,5-ジフルオロフェニル)エチニル-4-プロピル-2,6-ジフルオロベンゼンの合成
【００３０】
【化８】
上記（１）で得た4-プロピル-2,6-ジフルオロ-1-ヨードベンゼン44.2g及び1-エチニル-3,5-ジフルオロベンゼン30.9gをN,N-ジメチルホルムアミド140ml及びトリエチルアミン45mlに溶解した。テトラキス（トリフェニルホスフィン）パラジウム(0)1.5gとヨウ化銅(I)0.3gを加え、60℃で3時間攪拌した。室温にもどし、水50mlを加え、酢酸エチル100mlで抽出した。水、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、シリカゲルカラムクロマトグラフィー（溶媒：ヘキサン）を用いて精製し、1-(3,5-ジフルオロフェニル)エチニル-4-プロピル-2,6-ジフルオロベンゼン43.1gを得た。
（３） 1-(3,5-ジフルオロ-4-ヨードフェニル)エチニル-4-プロピル-2,6-ジフルオロベンゼンの合成
【００３２】
【化９】
上記（２）で得た1-(3,5-ジフルオロフェニル)エチニル-4-プロピル-2,6-ジフルオロベンゼン17.6gをテトラヒドロフラン70mlに溶解し、-50℃に冷却した。攪拌下液温-40℃を越えない速度でｎ−ブチルリチウムｎ−ヘキサン溶液(1.69mol/l)39mlを滴下し、さらに30分間攪拌した。ヨウ素16.8gのテトラヒドロフラン70ml溶液を液温が-40℃を越えない速度で滴下した。さらに30分間攪拌し、水10mlを加え室温にもどした。ヘキサン170mlを加え、10%亜硫酸水素ナトリウム水溶液、水、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、
1-(3,5-ジフルオロ-4-ヨードフェニル)エチニル-4-プロピル-2,6-ジフルオロベンゼン23.8gを得た。
（４） 4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,4,5-トリフルオロフェニル)エチニル-2,6-ジフルオロベンゼン（(No.1)の化合物）の合成
【００３４】
【化１０】
上記（３）で得た1-(3,5-ジフルオロ-4-ヨードフェニル)エチニル-4-プロピル-2,6-ジフルオロベンゼン10.0g及び1-エチニル-3,4,5-トリフルオロベンゼン5.6gをN,N-ジメチルホルムアミド40ml及びトリエチルアミン10mlに溶解した。テトラキス（トリフェニルホスフィン）パラジウム(0)0.17gとヨウ化銅(I)0.05gを加え、60℃で3時間攪拌した。室温にもどし、水50mlを加え、酢酸エチル100mlで抽出した。水、飽和食塩水で順次洗浄し、無水硫酸ナトリウムで乾燥した。溶媒を留去し、シリカゲルカラムクロマトグラフィー（溶媒：ヘキサン）を用いて精製し、さらにアセトンから再結晶し、4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,4,5-トリフルオロフェニル)エチニル-2,6-ジフルオロベンゼン1.8gを得た。この化合物の融点は、170.5℃であった。
【００３６】
同様にして、以下の化合物を得た。
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,4-ジフルオロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-クロロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオトメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ジフルオロメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオロメチル
フェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-シアノフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロピルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ペンチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロポキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,4,5-トリフルオロフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,4,5-トリフルオロフェニル)エチニル-ベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,4,5-トリフルオロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-フルオロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-クロロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-トリフルオトメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-ジフルオロメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-トリフルオロメチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-シアノフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-メチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-エチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-プロピルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-ブチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-ペンチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-メトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-エトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-プロポキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-ブトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,4-ジフルオロフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-クロロフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオトメトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ジフルオロメトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオロメチル
フェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-シアノフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロピルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ペンチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロポキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,4-ジフルオロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-クロロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオトメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ジフルオロメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオロメチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-シアノフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロピルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ペンチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロポキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,4,5-トリフルオロフェニル)エチニルベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,4,5-トリフルオロフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-フルオロフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-クロロフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-トリフルオトメトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-ジフルオロメトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-トリフルオロメチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-シアノフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-メチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-ジフルオロ-4-エチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-プロピルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-ブチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-ペンチルフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-メトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-エトキシフェニル)エチニル-2-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-プロポキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3-フルオロ-4-ブトキシフェニル)エチニル-2-フルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-クロロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-トリフルオトメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-ジフルオロメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-トリフルオロメチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-シアノフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-メチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-エチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-プロピルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-ブチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-ペンチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-メトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-エトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-プロポキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(4-ブトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,4-ジフルオロフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-クロロフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオトメトキシフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ジフルオロメトキシフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオロメチルフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-シアノフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メチルフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エチルフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロピルフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブチルフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ペンチルフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メトキシフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エトキシフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロポキシフェニル)エチニルベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブトキシフェニル)エチニルベンゼン
4-(4-プロルフェニル)エチニル-1-(3,4-ジフルオロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-クロロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオトメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-ジフルオロメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオロメチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-シアノフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-メチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-エチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-プロピルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-ブチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-ペンチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-メトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-エトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-プロポキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピルフェニル)エチニル-1-(3,5-ジフルオロ-4-ブトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,4-ジフルオロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-クロロフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオトメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ジフルオロメトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-トリフルオロメチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-シアノフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロピルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ペンチルフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2,6-ジフルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-メトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-エトキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-プロポキシフェニル)エチニル-2,6-ジフルオロベンゼン
4-(4-プロピル-2-フルオロフェニル)エチニル-1-(3,5-ジフルオロ-4-ブトキシフェニル)エチニル-2,6-ジフルオロベンゼン
（実施例２） 液晶組成物の調製
汎用のホスト液晶組成物（Ａ）を調製した。
【００３７】
【化１１】
この組成物の20℃で測定したΔn、Δε及びしきい値電圧は次の通りであった。
Δｎ： 0.092
Δε： 6.7
しきい値電圧： 1.60V
このホスト液晶（Ａ）９５重量％及び一般式（I）で表される化合物であり、実施例１で得た(No.1)の化合物
【００３９】
【化１２】
５重量％からなる液晶組成物（Ａ−１）を調製し、同様にΔｎ、Δε及びしきい値電圧を測定したところ以下の通りであった。
Δｎ： 0.097
Δε： 7.0
しきい値電圧： 1.50V
従って、(No.1)の化合物は5重量％といった少ない混合量にもかかわらず、Δｎ及びΔεを大きくし、しかもしきい値電圧を大きく低下させていることがわかる。
（比較例）
式（ａ）
【００４１】
【化１３】
の化合物５重量％及びホスト液晶（Ａ）９５重量％からなる比較液晶組成物（Ａ−ａ）を調製し、同様に測定したΔｎ、Δε、しきい値電圧は以下の通りであった。
【００４３】
Δｎ： 0.097
Δε： 6.8
しきい値電圧： 1.55V
従って、Δｎについては式（ａ）の化合物は、本発明の一般式（Ｉ）で表される（Ｎｏ．１）の化合物と同様の効果を有するが、（Ｎｏ．１）の化合物のほうが、Δεを大きくし、よりしきい値電圧を低減させる効果を有していることが理解できる。
【００４４】
【発明の効果】
本発明により提供される化合物は、実施例にも示したように工業的にも容易に製造することができる。この得られたΔεの極めて大きい化合物は、少量の添加にもかかわらず組成物のΔｎを大きくすることができ、且つ従来用いられている液晶性化合物と比較してもしきい値電圧の低減効果に優れるため、それを含有する液晶組成物は、特に高速応答と低電圧駆動を必要とする実用的液晶表示用材料としてきわめて有用である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a novel liquid crystal compound having a very large dielectric anisotropy that is useful as an electro-optical liquid crystal display material, and a liquid crystal composition containing the novel liquid crystal compound.
[0002]
[Prior art]
Liquid crystal display elements are used as information display elements such as clocks, calculators, word processors, personal computer displays, and the like, and are becoming increasingly important as an interface between electronic devices and people.
[0003]
Display systems using liquid crystals are roughly classified into three types: a field effect (FEM) type, a dynamic scattering (DSM) type, and a thermal effect (TEM) type. Various display systems have been proposed using these effects. Up to now, display systems using the field effect type have been put into practical use. Field effect types include twisted nematic (TN), super twisted nematic (STN), guest-host (GH), electric field controlled birefringence (ECB), and cholesteric-nematic phase transition (CN-PT). Type, surface stabilized ferroelectric liquid crystal (SSFLC) type, and the like. Among them, the TN type and STN type are currently mainstream. Among them, in the STN type, the display capacity can be increased to some extent due to the improvement of the driving method and the like. However, the demand for large display capacity and display quality in recent years is no longer limited. Therefore, an active matrix method such as a MIM (Metal Insulator Metal) method using a two-terminal nonlinear element having a threshold characteristic for each display pixel and a TFT (Thin Film Transistor) method using a three-terminal active element has been put into practical use. It is rapidly developing for larger capacity.
[0004]
The liquid crystal materials used in these liquid crystal display systems are required to have various characteristics depending on the characteristics of each display system. However, the low drive voltage and the high response speed are common. This is a particularly important requirement.
[0005]
In order to reduce the drive voltage, a compound having a large dielectric anisotropy (Δε) that reduces the threshold voltage is required. In order to increase this Δε, it is necessary to introduce more polar groups such as fluorine atoms in the same direction in addition to the terminal polar group.
[0006]
The response time can be shortened by reducing the viscosity of the liquid crystal composition, but can also be achieved by reducing the cell thickness of the device. However, since the product (Δn · d) of the cell thickness (d) and the refractive index anisotropy (Δn) is set to a constant value, a liquid crystal material having a large Δn is required to reduce d. . In addition, a compound having a large Δn is also required for a polymer-dispersed liquid crystal display element that requires strong cloudiness.
[0007]
Currently, as a compound having a large Δn and a large Δε, for example, a tolan derivative of the formula (a) is known.
[0008]
[Chemical 2]
The compound of the formula (a) has large Δn and Δε, and mixing them can increase Δn of the composition and reduce the threshold voltage. However, the degree was not fully satisfactory.
[0010]
Therefore, a compound that can increase Δn and Δε more effectively by mixing is desired.
[0011]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a novel liquid crystalline compound having a large Δn and Δε and a liquid crystal composition having a large Δn and a low threshold voltage by using this liquid crystalline compound. .
[0012]
[Means for Solving the Problems]
As a result of intensive studies in order to solve the above problems, the present invention has the general formula (I)
[0013]
[Chemical 3]
(In the formula, R represents an alkyl group having 1 to 10 carbon atoms; Y 1 , Y 2 , Y Three , Y Four , Y Five And Y 6 Each independently represents a hydrogen atom or a fluorine atom, at least four of which represent a fluorine atom, Z represents a fluorine atom, a chlorine atom, a trifluoromethoxy group, a difluoromethoxy group, a trifluoromethyl group, a cyano group, a carbon atom Represents an alkyl group or an alkoxyl group of formula 1 to 10; ) And a liquid crystal composition containing the compound have been found as means for solving the above problems.
[0015]
DETAILED DESCRIPTION OF THE INVENTION
An example of the liquid crystalline compound of the present invention will be described below.
In the general formula (I), Z is preferably a fluorine atom or a trifluoromethoxy group, and particularly preferably a fluorine atom in order to increase Δε and provide versatility. In this case, R is preferably a linear alkyl group having 1 to 7 carbon atoms, and more preferably a linear alkyl group having 2 to 5 carbon atoms. Y 1 , Y 2 , Y Three , Y Four , Y Five And Y 6 It is preferable that 5 or more are fluorine atoms.
[0016]
The compound represented by the general formula (I) according to the present invention can be produced, for example, as follows.
[0017]
[Formula 4]
(In the above formulas (I) to (VII), R, Y 1 , Y 2 , Y Three , Y Four , Y Five , Y 6 And Z represent the same meaning as in general formula (I), and Q 1 , Q 2 Represents a bromine or iodine atom. )
First step: direct bromination or iodination of the compound of general formula (II), or Y Five , Y 6 When both are fluorine atoms, the compound of the general formula (III) is produced by lithiation with a lithiation agent such as n-butyllithium and then reacting with bromine or iodine.
2nd process: The compound of general formula (V) is manufactured by making the compound of general formula (III) and general formula (IV) react in presence of a palladium catalyst and a copper catalyst.
Third step: Bromine or iodination of the compound of the general formula (V) directly or after protecting the triple bond, or Y Three , Y Four When both are fluorine atoms, the compound of the general formula (VI) is produced by lithiation with a lithiating agent such as n-butyllithium and then reacting with bromine or iodine. Alternatively, in the second step, a compound in which the 4-position is substituted with an amino group or the like may be used instead of the compound of the general formula (IV), and then the substituent may be converted to bromine or iodine.
Fourth step: The compound of the general formula (I) of the present invention is produced by reacting the compound of the general formula (VI) and the general formula (VII) in the presence of a palladium catalyst and a copper catalyst.
[0019]
The representative compound represented by the general formula (I) thus produced is shown.
[0020]
[Chemical formula 5]
Melting point: 170.5 ° C
5% by weight of the compound (No. 1) represented by the general formula (I) of the present invention and a host liquid crystal (A) which is currently widely used
[0022]
[Chemical 6]
(In the formula, the cyclohexane ring is in a trans configuration.)
When a liquid crystal composition (A-1) consisting of 95% by weight was prepared, Δn of this composition was 0.097, Δε was 7.0, and the threshold voltage was 1.50V. Since Δn of the host liquid crystal (A) is 0.092, Δε is 6.7, and the threshold voltage is 1.60 V, Δn and Δε are greatly increased despite the slight addition, and the threshold voltage is increased. The value voltage could be reduced by 0.1V.
[0024]
For comparison, a comparative composition (Aa) comprising 5% by weight of the compound of the formula (a) shown above and 95% by weight of the host liquid crystal (A) was prepared. When measured in the same manner, Δn was 0.097, which was about the same as (A-1), but Δε increased only to 6.8, the threshold voltage was 1.55 V, and the host liquid crystal (A ) And only 0.05V.
[0025]
From the above, the compound represented by the general formula (I) according to the present invention can effectively increase Δn and Δε and lower the threshold voltage with a small addition to the host liquid crystal. It can be easily understood that the effect is superior to conventional compounds.
[0026]
The present invention thus also provides a liquid crystal composition containing the compound represented by the general formula (I).
As a preferable representative example of the nematic liquid crystal compound that can be used as the liquid crystal composition by mixing with the compound represented by the general formula (I) as described above, for example, 4-substituted benzoic acid-4- Substituted phenyl, 4-substituted cyclohexanecarboxylic acid-4-substituted phenyl, 4-substituted cyclohexanecarboxylic acid-4-substituted biphenyl, 4- (4-substituted hexanehexanecarbonyloxy) benzoic acid-4-substituted phenyl, 4- (4 -Substituted cyclohexyl) benzoic acid-4-substituted phenyl, 4- (4-substituted cyclohexyl) benzoic acid-4-substituted cyclohexyl, 4,4-substituted biphenyl, 1- (4-substituted phenyl) -4-substituted cyclohexane, 4 , 4-substituted terphenyl, 1- (4-substituted biphenylyl) -4-substituted cyclohexane, 1- (4-substituted cyclohexyl) -4- (4-substituted phenyl) cyclohexane, 2- (4-substituted phenyl) -5 -Substituted pyrimidine, 2- (4-substituted biphenylyl)- 5-substituted pyrimidine, 1- (4-substituted cyclohexyl) -2- (4-substituted cyclohexyl) ethane, 1- [4- (4-substituted cyclohexyl) cyclohexyl] -2- (4-substituted phenyl) ethane, 1- [4- (4-substituted phenyl) cyclohexyl] -2- (4-substituted cyclohexyl) ethane, 1- (4-substituted phenyl) -2- (4-substituted phenyl) ethyne, 1- [4- (4-substituted Cyclohexyl)]-2- (4-substituted phenyl) ethyne, and compounds in which the benzene ring is laterally fluorine substituted with the above compound.
[0027]
【Example】
The following examples further illustrate the present invention. However, the present invention is not limited to these examples.
Example 1 4- (4-Propyl-2,6-difluorophenyl) ethynyl-1- (3,4,5-trifluorophenyl) ethynyl-2,6-difluorobenzene (Compound of (No. 1) )
(In the general formula (I), R is a propyl group, Z, Y 1 , Y 2 , Y Three , Y Four , Y Five And Y 6 Of fluorine atoms)
(1) Synthesis of 4-propyl-2,6-difluoro-1-iodobenzene
[0028]
[Chemical 7]
30 g of 3,5-difluoro-1-propylbenzene was dissolved in 120 ml of tetrahydrofuran and cooled to -50 ° C. Under stirring, 125 ml of n-butyllithium n-hexane solution (1.69 mol / l) was added dropwise at such a rate that the liquid temperature did not exceed -40 ° C, and the mixture was further stirred for 30 minutes. A solution of iodine (53.7 g) in tetrahydrofuran (220 ml) was added dropwise at a rate such that the liquid temperature did not exceed -40 ° C. The mixture was further stirred for 30 minutes, and 10 ml of water was added to return to room temperature. 150 ml of hexane was added, washed successively with 10% aqueous sodium bisulfite solution, water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 54.7 g of 4-propyl-2,6-difluoro-1-iodobenzene.
(2) Synthesis of 1- (3,5-difluorophenyl) ethynyl-4-propyl-2,6-difluorobenzene
[0030]
[Chemical 8]
44.2 g of 4-propyl-2,6-difluoro-1-iodobenzene and 30.9 g of 1-ethynyl-3,5-difluorobenzene obtained in (1) above were dissolved in 140 ml of N, N-dimethylformamide and 45 ml of triethylamine. . Tetrakis (triphenylphosphine) palladium (0) 1.5 g and copper iodide (I) 0.3 g were added, and the mixture was stirred at 60 ° C. for 3 hours. The temperature was returned to room temperature, 50 ml of water was added, and the mixture was extracted with 100 ml of ethyl acetate. The extract was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified using silica gel column chromatography (solvent: hexane) to obtain 43.1 g of 1- (3,5-difluorophenyl) ethynyl-4-propyl-2,6-difluorobenzene.
(3) Synthesis of 1- (3,5-difluoro-4-iodophenyl) ethynyl-4-propyl-2,6-difluorobenzene
[0032]
[Chemical 9]
17.6 g of 1- (3,5-difluorophenyl) ethynyl-4-propyl-2,6-difluorobenzene obtained in (2) above was dissolved in 70 ml of tetrahydrofuran and cooled to -50 ° C. Under stirring, 39 ml of n-butyllithium n-hexane solution (1.69 mol / l) was added dropwise at a rate not exceeding -40 ° C, and the mixture was further stirred for 30 minutes. A solution of iodine (16.8 g) in tetrahydrofuran (70 ml) was added dropwise at a rate such that the liquid temperature did not exceed -40 ° C. The mixture was further stirred for 30 minutes, and 10 ml of water was added to return to room temperature. 170 ml of hexane was added, washed successively with 10% aqueous sodium bisulfite solution, water and saturated brine, and dried over anhydrous sodium sulfate. Evaporate the solvent,
23.8 g of 1- (3,5-difluoro-4-iodophenyl) ethynyl-4-propyl-2,6-difluorobenzene was obtained.
(4) 4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,4,5-trifluorophenyl) ethynyl-2,6-difluorobenzene (compound of (No. 1)) Composition
[0034]
[Chemical Formula 10]
10.0 g of 1- (3,5-difluoro-4-iodophenyl) ethynyl-4-propyl-2,6-difluorobenzene obtained in the above (3) and 5.6 of 1-ethynyl-3,4,5-trifluorobenzene g was dissolved in 40 ml of N, N-dimethylformamide and 10 ml of triethylamine. Tetrakis (triphenylphosphine) palladium (0) 0.17 g and copper iodide (I) 0.05 g were added, and the mixture was stirred at 60 ° C. for 3 hours. The temperature was returned to room temperature, 50 ml of water was added, and the mixture was extracted with 100 ml of ethyl acetate. The extract was washed successively with water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was distilled off, the residue was purified using silica gel column chromatography (solvent: hexane), recrystallized from acetone, and 4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,4 , 5-trifluorophenyl) ethynyl-2,6-difluorobenzene (1.8 g) was obtained. The melting point of this compound was 170.5 ° C.
[0036]
In the same manner, the following compound was obtained.
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,4-difluorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-chlorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-difluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethyl
Phenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-cyanophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-methylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-ethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-propylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-butylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-pentylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-methoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-ethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-propoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-butoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,4,5-trifluorophenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,4,5-trifluorophenyl) ethynyl-benzene
4- (4-Propylphenyl) ethynyl-1- (3,4,5-trifluorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-fluorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-chlorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-trifluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-difluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-trifluoromethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-cyanophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-methylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-ethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-propylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-butylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-pentylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-methoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-ethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-propoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-butoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,4-difluorophenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-chlorophenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-difluoromethoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethyl
Phenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-cyanophenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-methylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-ethylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-propylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-butylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-pentylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-methoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-ethoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-propoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-butoxyphenyl) ethynyl-2-fluorobenzene
4- (4-Propyl-2-fluorophenyl) ethynyl-1- (3,4-difluorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-chlorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-difluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-cyanophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-methylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-ethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-propylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-butylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-pentylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-methoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-ethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-propoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-butoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propyl-2-fluorophenyl) ethynyl-1- (3,4,5-trifluorophenyl) ethynylbenzene
4- (4-Propylphenyl) ethynyl-1- (3,4,5-trifluorophenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-fluorophenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-chlorophenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-trifluoromethoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-difluoromethoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-trifluoromethylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-cyanophenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-methylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-difluoro-4-ethylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-propylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-butylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-pentylphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-methoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-ethoxyphenyl) ethynyl-2-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-propoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3-fluoro-4-butoxyphenyl) ethynyl-2-fluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-chlorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-trifluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-difluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-trifluoromethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-cyanophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-methylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-ethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-propylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-butylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-pentylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-methoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-ethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-propoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (4-butoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,4-difluorophenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-chlorophenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethoxyphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-difluoromethoxyphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethylphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-cyanophenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-methylphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-ethylphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-propylphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-butylphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-pentylphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-methoxyphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-ethoxyphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-propoxyphenyl) ethynylbenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-butoxyphenyl) ethynylbenzene
4- (4-Prolphenyl) ethynyl-1- (3,4-difluorophenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-chlorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propylphenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propylphenyl) ethynyl-1- (3,5-difluoro-4-difluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propylphenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-cyanophenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-methylphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-ethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-propylphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-butylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propylphenyl) ethynyl-1- (3,5-difluoro-4-pentylphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-methoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-ethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propylphenyl) ethynyl-1- (3,5-difluoro-4-propoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propylphenyl) ethynyl-1- (3,5-difluoro-4-butoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-Propyl-2-fluorophenyl) ethynyl-1- (3,4-difluorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-chlorophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-difluoromethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-trifluoromethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-cyanophenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-methylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-ethylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-propylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-butylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-pentylphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2,6-difluorophenyl) ethynyl-1- (3,5-difluoro-4-methoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-ethoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-propoxyphenyl) ethynyl-2,6-difluorobenzene
4- (4-propyl-2-fluorophenyl) ethynyl-1- (3,5-difluoro-4-butoxyphenyl) ethynyl-2,6-difluorobenzene
(Example 2) Preparation of liquid crystal composition
A general-purpose host liquid crystal composition (A) was prepared.
[0037]
Embedded image
The Δn, Δε and threshold voltage of this composition measured at 20 ° C. were as follows.
Δn: 0.092
Δε: 6.7
Threshold voltage: 1.60V
Compound (No. 1) obtained in Example 1, which is a compound represented by 95% by weight of the host liquid crystal (A) and the general formula (I)
[0039]
Embedded image
A liquid crystal composition (A-1) consisting of 5% by weight was prepared, and Δn, Δε and threshold voltage were measured in the same manner as follows.
Δn: 0.097
Δε: 7.0
Threshold voltage: 1.50V
Therefore, it can be seen that the compound of (No. 1) increases Δn and Δε and lowers the threshold voltage greatly despite the small mixing amount of 5% by weight.
(Comparative example)
Formula (a)
[0041]
Embedded image
A comparative liquid crystal composition (A-a) comprising 5% by weight of the above compound and 95% by weight of the host liquid crystal (A) was prepared, and Δn, Δε and threshold voltage measured in the same manner were as follows.
[0043]
Δn: 0.097
Δε: 6.8
Threshold voltage: 1.55V
Therefore, for Δn, the compound of formula (a) has the same effect as the compound of (No. 1) represented by the general formula (I) of the present invention, but the compound of (No. 1) is more It can be understood that Δε is increased and the threshold voltage is further reduced.
[0044]
【The invention's effect】
The compounds provided by the present invention can be easily produced industrially as shown in the Examples. The obtained compound having a very large Δε can increase the Δn of the composition in spite of the addition of a small amount, and is effective in reducing the threshold voltage even when compared with a liquid crystal compound used conventionally. Since it is excellent, the liquid crystal composition containing it is extremely useful as a practical liquid crystal display material that requires a high-speed response and low-voltage driving.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20470896A JP3900554B2 (en) | 1996-08-02 | 1996-08-02 | Liquid crystalline compounds with extremely large dielectric anisotropy |
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| Application Number | Priority Date | Filing Date | Title |
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| JP20470896A JP3900554B2 (en) | 1996-08-02 | 1996-08-02 | Liquid crystalline compounds with extremely large dielectric anisotropy |
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| Publication Number | Publication Date |
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| JPH1045642A JPH1045642A (en) | 1998-02-17 |
| JP3900554B2 true JP3900554B2 (en) | 2007-04-04 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9777217B2 (en) | 2011-03-24 | 2017-10-03 | Merck Patent Gmbh | Compounds having a C—C triple bond |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001329264A (en) * | 2000-05-24 | 2001-11-27 | Sumitomo Chem Co Ltd | Liquid crystal composition containing benzylidynyltolan compound and liquid crystal element using the same |
| US6838017B1 (en) * | 2000-09-05 | 2005-01-04 | Hrl Laboratories, Llc | Polar tolane liquid crystals |
| WO2011087130A1 (en) * | 2010-01-18 | 2011-07-21 | 株式会社クラレ | Acetylene compound and organic semiconductor material comprising same |
| WO2012005310A1 (en) * | 2010-07-08 | 2012-01-12 | 旭硝子株式会社 | Fluorinated aromatic compound, organic semiconductor material, and organic thin-film device |
| CN103059875A (en) * | 2011-10-24 | 2013-04-24 | 财团法人工业技术研究院 | Liquid crystal compound and liquid crystal display comprising same |
| US8722156B2 (en) | 2011-10-24 | 2014-05-13 | Industrial Technology Research Institute | Liquid crystal compound and liquid crystal display |
| CN103130649B (en) * | 2011-10-24 | 2014-10-22 | 财团法人工业技术研究院 | Liquid crystal compound and liquid crystal display |
| CN102557896B (en) * | 2011-12-15 | 2015-03-11 | 石家庄诚志永华显示材料有限公司 | (Poly) fluorine substituted phenyl diacetylene (bi) phenyl derivative, and preparation method and application thereof |
| CN102617303B (en) * | 2012-02-20 | 2014-05-28 | 石家庄诚志永华显示材料有限公司 | Multi-fluorine substituted bi-(phenyl acetenyl) benzene derivative, preparation method thereof and application |
| WO2014044357A1 (en) * | 2012-09-21 | 2014-03-27 | Merck Patent Gmbh | Compounds having a c-c triple bond and use thereof in liquid-crystal mixtures |
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1996
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9777217B2 (en) | 2011-03-24 | 2017-10-03 | Merck Patent Gmbh | Compounds having a C—C triple bond |
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