JP3569935B2 - Fluorotran derivative - Google Patents
Fluorotran derivative Download PDFInfo
- Publication number
- JP3569935B2 JP3569935B2 JP29976293A JP29976293A JP3569935B2 JP 3569935 B2 JP3569935 B2 JP 3569935B2 JP 29976293 A JP29976293 A JP 29976293A JP 29976293 A JP29976293 A JP 29976293A JP 3569935 B2 JP3569935 B2 JP 3569935B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- general formula
- trans
- liquid crystal
- cyclohexyl
- 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 claims description 87
- 239000004973 liquid crystal related substance Substances 0.000 claims description 58
- 239000000203 mixture Substances 0.000 claims description 40
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000001153 fluoro group Chemical group F* 0.000 claims description 13
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 12
- 229910052731 fluorine Chemical group 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000004183 alkoxy alkyl group Chemical group 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 description 67
- 230000015572 biosynthetic process Effects 0.000 description 52
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 39
- -1 4-substituted benzoic acid 4-substituted phenyl ester Chemical class 0.000 description 33
- 239000002904 solvent Substances 0.000 description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 239000012071 phase Substances 0.000 description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 239000012044 organic layer Substances 0.000 description 14
- SQYYCSHUGCWURO-UHFFFAOYSA-N 1,3-difluoro-2-iodo-5-(4-propylcyclohexyl)benzene Chemical compound C1CC(CCC)CCC1C1=CC(F)=C(I)C(F)=C1 SQYYCSHUGCWURO-UHFFFAOYSA-N 0.000 description 13
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 239000007795 chemical reaction product Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].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 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- 238000010992 reflux Methods 0.000 description 9
- 238000010898 silica gel chromatography Methods 0.000 description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 7
- 229910052740 iodine Chemical group 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 6
- NQEDLIZOPMNZMC-UHFFFAOYSA-N 4-propylcyclohexan-1-one Chemical compound CCCC1CCC(=O)CC1 NQEDLIZOPMNZMC-UHFFFAOYSA-N 0.000 description 6
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 6
- HKJCELUUIFFSIN-UHFFFAOYSA-N 5-bromo-1,2,3-trifluorobenzene Chemical compound FC1=CC(Br)=CC(F)=C1F HKJCELUUIFFSIN-UHFFFAOYSA-N 0.000 description 5
- GENVTRUAZLLBGY-HAQNSBGRSA-N C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(I)C(F)=C1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1C1=CC=C(I)C(F)=C1 GENVTRUAZLLBGY-HAQNSBGRSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 0 *C(CC1)CCC1C(C(CC1)CCC1c1cc(*)c(*)c(*)c1)N Chemical compound *C(CC1)CCC1C(C(CC1)CCC1c1cc(*)c(*)c(*)c1)N 0.000 description 4
- GHOUEKQRKXYGHJ-UHFFFAOYSA-N 1,3-difluoro-5-(4-propylcyclohexyl)benzene Chemical compound C1CC(CCC)CCC1C1=CC(F)=CC(F)=C1 GHOUEKQRKXYGHJ-UHFFFAOYSA-N 0.000 description 4
- BWGLDRGCGYNRKT-UHFFFAOYSA-N 1-fluoro-3-(4-propylcyclohexen-1-yl)benzene Chemical compound C1C(CCC)CCC(C=2C=C(F)C=CC=2)=C1 BWGLDRGCGYNRKT-UHFFFAOYSA-N 0.000 description 4
- FATSUROKEGFTEZ-UHFFFAOYSA-N 2-methyl-4-(3,4,5-trifluorophenyl)but-3-yn-2-ol Chemical compound CC(C)(C#CC1=CC(=C(C(=C1)F)F)F)O FATSUROKEGFTEZ-UHFFFAOYSA-N 0.000 description 4
- BZXWRVPVZZZAKB-UHFFFAOYSA-N 5-ethynyl-1,2,3-trifluorobenzene Chemical compound FC1=CC(C#C)=CC(F)=C1F BZXWRVPVZZZAKB-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- PGOGNCXMCLRCEL-GARHLSDISA-N C(CC)[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)C1=CC(=C(C(=C1)F)I)F Chemical compound C(CC)[C@@H]1CC[C@H](CC1)[C@@H]1CC[C@H](CC1)C1=CC(=C(C(=C1)F)I)F PGOGNCXMCLRCEL-GARHLSDISA-N 0.000 description 4
- UCPPGQWSQUGPEY-JOCQHMNTSA-N C1C[C@@H](CCC)CC[C@@H]1C1=CC=CC(F)=C1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1C1=CC=CC(F)=C1 UCPPGQWSQUGPEY-JOCQHMNTSA-N 0.000 description 4
- KPHKQXNCNXVTKF-WKILWMFISA-N CCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1C#CC(C)(C)O Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1C#CC(C)(C)O KPHKQXNCNXVTKF-WKILWMFISA-N 0.000 description 4
- DTFTZCNGZPGOEQ-CTYIDZIISA-N CCC[C@H]1CC[C@@H](CC1)c1ccc(C#C)c(F)c1 Chemical compound CCC[C@H]1CC[C@@H](CC1)c1ccc(C#C)c(F)c1 DTFTZCNGZPGOEQ-CTYIDZIISA-N 0.000 description 4
- YDWNNZGVXZHCNJ-SAABIXHNSA-N COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC=C1C#C Chemical compound COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC=C1C#C YDWNNZGVXZHCNJ-SAABIXHNSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical class C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 239000011630 iodine Substances 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- ZEVDXVPFQNRKEO-UHFFFAOYSA-N 1,3-difluoro-5-(4-propylcyclohexen-1-yl)benzene Chemical compound C1C(CCC)CCC(C=2C=C(F)C=C(F)C=2)=C1 ZEVDXVPFQNRKEO-UHFFFAOYSA-N 0.000 description 3
- QDFKKJYEIFBEFC-UHFFFAOYSA-N 1-bromo-3-fluorobenzene Chemical compound FC1=CC=CC(Br)=C1 QDFKKJYEIFBEFC-UHFFFAOYSA-N 0.000 description 3
- OSTVHWGRCHADDW-UHFFFAOYSA-N 4-(3-methoxypropyl)cyclohexan-1-one Chemical compound COCCCC1CCC(=O)CC1 OSTVHWGRCHADDW-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- GZZXAKIQARJTKD-JCNLHEQBSA-N CCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1C#CC(C=C1F)=CC(F)=C1F Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1C#CC(C=C1F)=CC(F)=C1F GZZXAKIQARJTKD-JCNLHEQBSA-N 0.000 description 3
- MFCDWGTVRZGQII-KOMQPUFPSA-N CCC[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1C#CC(C=C1F)=CC(F)=C1F Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1C#CC(C=C1F)=CC(F)=C1F MFCDWGTVRZGQII-KOMQPUFPSA-N 0.000 description 3
- GZHJTMBOKPHONH-JOCQHMNTSA-N COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1I Chemical compound COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1I GZHJTMBOKPHONH-JOCQHMNTSA-N 0.000 description 3
- CAQAKRIWXODWNZ-IRJFHVNHSA-N COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC=C1C#CC(C=C1F)=CC(F)=C1F Chemical compound COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC=C1C#CC(C=C1F)=CC(F)=C1F CAQAKRIWXODWNZ-IRJFHVNHSA-N 0.000 description 3
- VSYYFBIECYFWFJ-HDJSIYSDSA-N COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC=C1I Chemical compound COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC=C1I VSYYFBIECYFWFJ-HDJSIYSDSA-N 0.000 description 3
- CWRDOGRHYHRGOO-HAQNSBGRSA-N COCCC[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1I Chemical compound COCCC[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1I CWRDOGRHYHRGOO-HAQNSBGRSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005669 field effect Effects 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 3
- 239000012264 purified product Substances 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 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 2
- JHLKSIOJYMGSMB-UHFFFAOYSA-N 1-bromo-3,5-difluorobenzene Chemical compound FC1=CC(F)=CC(Br)=C1 JHLKSIOJYMGSMB-UHFFFAOYSA-N 0.000 description 2
- QPJKIRNIIXIPIE-UHFFFAOYSA-N 5-bromo-1,3-difluoro-2-(trifluoromethyl)benzene Chemical compound FC1=CC(Br)=CC(F)=C1C(F)(F)F QPJKIRNIIXIPIE-UHFFFAOYSA-N 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N Acetylene Chemical compound C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- NTBLQHSPSVUDTN-KOMQPUFPSA-N CCC[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1C#CC1=CC(F)=C(C(F)(F)F)C(F)=C1 Chemical compound CCC[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1C#CC1=CC(F)=C(C(F)(F)F)C(F)=C1 NTBLQHSPSVUDTN-KOMQPUFPSA-N 0.000 description 2
- ALOCSBYEMRSACG-XHPGVBHPSA-N CCC[C@H](CC1)CC[C@@H]1[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1C#CC(C=C1F)=CC(F)=C1F Chemical compound CCC[C@H](CC1)CC[C@@H]1[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1C#CC(C=C1F)=CC(F)=C1F ALOCSBYEMRSACG-XHPGVBHPSA-N 0.000 description 2
- AHWUJTVLHFICBY-SAABIXHNSA-N COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1C#CC1=CC(F)=C(C(F)(F)F)C(F)=C1 Chemical compound COCCC[C@H](CC1)CC[C@@H]1C(C=C1)=CC(F)=C1C#CC1=CC(F)=C(C(F)(F)F)C(F)=C1 AHWUJTVLHFICBY-SAABIXHNSA-N 0.000 description 2
- ZYRGDSPDTZAZPV-JCNLHEQBSA-N COCCC[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1C#CC(C=C1F)=CC(F)=C1F Chemical compound COCCC[C@H](CC1)CC[C@@H]1C(C=C1F)=CC(F)=C1C#CC(C=C1F)=CC(F)=C1F ZYRGDSPDTZAZPV-JCNLHEQBSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000004988 Nematic liquid crystal Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- KJIFKLIQANRMOU-UHFFFAOYSA-N oxidanium;4-methylbenzenesulfonate Chemical compound O.CC1=CC=C(S(O)(=O)=O)C=C1 KJIFKLIQANRMOU-UHFFFAOYSA-N 0.000 description 2
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- AJKNNUJQFALRIK-UHFFFAOYSA-N 1,2,3-trifluorobenzene Chemical compound FC1=CC=CC(F)=C1F AJKNNUJQFALRIK-UHFFFAOYSA-N 0.000 description 1
- KSASJELKLBIMSG-UHFFFAOYSA-N 1,2-difluoro-4-iodobenzene Chemical compound FC1=CC=C(I)C=C1F KSASJELKLBIMSG-UHFFFAOYSA-N 0.000 description 1
- QANDOICOKGBRHR-UHFFFAOYSA-N 1-fluoro-2-(2-phenylethynyl)benzene Chemical class FC1=CC=CC=C1C#CC1=CC=CC=C1 QANDOICOKGBRHR-UHFFFAOYSA-N 0.000 description 1
- 125000004211 3,5-difluorophenyl group Chemical group [H]C1=C(F)C([H])=C(*)C([H])=C1F 0.000 description 1
- AKCZQKBKWXBJOF-UHFFFAOYSA-N 4-(4-propylcyclohexyl)cyclohexan-1-one Chemical compound C1CC(CCC)CCC1C1CCC(=O)CC1 AKCZQKBKWXBJOF-UHFFFAOYSA-N 0.000 description 1
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 1
- SQYYCSHUGCWURO-XYPYZODXSA-N CCC[C@H]1CC[C@@H](CC1)c1cc(F)c(I)c(F)c1 Chemical compound CCC[C@H]1CC[C@@H](CC1)c1cc(F)c(I)c(F)c1 SQYYCSHUGCWURO-XYPYZODXSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 239000004983 Polymer Dispersed Liquid Crystal Substances 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 210000002858 crystal cell Anatomy 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000000664 diazo group Chemical group [N-]=[N+]=[*] 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 239000012769 display material Substances 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 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
- 239000012212 insulator Substances 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- VOVZXURTCKPRDQ-CQSZACIVSA-N n-[4-[chloro(difluoro)methoxy]phenyl]-6-[(3r)-3-hydroxypyrrolidin-1-yl]-5-(1h-pyrazol-5-yl)pyridine-3-carboxamide Chemical compound C1[C@H](O)CCN1C1=NC=C(C(=O)NC=2C=CC(OC(F)(F)Cl)=CC=2)C=C1C1=CC=NN1 VOVZXURTCKPRDQ-CQSZACIVSA-N 0.000 description 1
- 230000000802 nitrating effect Effects 0.000 description 1
- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 1
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- CHKVPAROMQMJNQ-UHFFFAOYSA-M potassium bisulfate Chemical compound [K+].OS([O-])(=O)=O CHKVPAROMQMJNQ-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
Description
【０００１】
【産業上の利用分野】
本発明は電気光学的表示材料として有用な、新規なフルオロトラン誘導体である液晶化合物に関する。
【０００２】
【従来の技術】
液晶表示素子は、時計、電卓をはじめとして、最近では、ワープロ、コンピュータ端末ディスプレイ等、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ースとして重要性を増してきている。
【０００３】
液晶を用いた表示方式は、（１）電界効果（ＦＥＭ）型、（２）動的散乱（ＤＳＭ）型及び（３）熱効果（ＴＥＭ）型の３つに大別される。これらの効果を利用して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、ある程度までは容量の増加は可能となったが、近年の大表示容量要求に対してはもはや限界となった。そこで、表示画素ごとに、しきい特性をもつ非線形素子を用いる表示方式、例えば、ＭＩＭ（Ｍｅｔａｌ Ｉｎｓｕｒａｔｏｒ Ｍｅｔａｌ）方式、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つつある。
【０００４】
これらの液晶表示方式に用いられる液晶材料には、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、広い温度範囲で動作可能なこと、低電圧駆動が可能であること及び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。低電圧駆動を満足させるためには、液晶組成物に混合した際に、しきい値電圧を低下させる化合物が必要であり、広い温度範囲で駆動を可能とするためには、ネマチック相−等方性液体相転移温度（以下、Ｎ−Ｉ点という。）を上昇させる化合物が必要である。
【０００５】
応答時間を速くするためには、液晶組成物の粘度を低くすることが必要であるが、以下のような方法によっても応答時間を速くすることが可能である。
【０００６】
液晶表示ＴＮ型セルにおいて、セルの厚さをｄ（μｍ）、応答時間をτとすると、ｄ２とτとの間で比例関係があり、ｄの値を小さくすることにより応答時間の速い液晶セルを得ることができる。しかしながら、セル外観を損なう原因となるセル表面での干渉縞の発生を防止するために、セルに充填させる液晶材料の屈折率異方性（Δｎ）とセルの厚さ（ｄ）μｍの積（ｄ・Δｎ）をある特定の値に設定する必要がある。実用的に使用される液晶セルでは、Δｎ・ｄの値が０．５、１．０、１．６又は２．２のいずれかに設定されている。このようにΔｎ・ｄの値が一定値に設定されているため、ｄを小さくして応答を高速化するためには、Δｎの値の大きな液晶材料が必要である。
【０００７】
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の大きな液晶材料が有効である。
【０００８】
従って、Ｎ−Ｉ点が高く、Δｎの値が大きく、且つ組成物のしきい値電圧を低下させることが可能な化合物は、上記要求を満足させる液晶組成物の調製のために非常に重要であることが理解できるが、しかしながら、そのような化合物は、ほとんど知られていなかった。
【０００９】
このような点に基づいて検討を行った結果、最近本発明者らは、Ｎ−Ｉ点が高く、Δｎの値が大きく、且つ組成物のしきい値電圧を低下させることが可能な式（ａ）及び式（ｂ）
【００１０】
【化４】
の化合物を見いだした。（特願平４−１９２０６５号）しかしながら、上記の式（ａ）及び式（ｂ）の化合物は、現在汎用されている母体液晶に混合した際、Δｎ及びＮ−Ｉ点を十分に上昇させるものの、しきい値電圧については、決して充分満足できるものとはいえず、更に改良が必要であった。
【００１２】
【発明が解決しようとする問題点】
本発明が解決しようとする課題は、液晶組成物に混合した際に、Ｎ−Ｉ点を上昇させ、Δｎを大きくし、且つしきい値電圧を効果的に低下させる新規化合物、及びこの化合物を含有する液晶組成物を提供することにあり、また、その化合物の合成中間体として有用な化合物を提供することにある。
【００１３】
【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、一般式（Ｉ）
【００１４】
【化５】
（式中、Ｒは炭素原子数１〜１０の直鎖状アルキル基又は炭素原子数２〜１７の直鎖状アルコキシアルキルを表わし、好ましくは炭素原子数２〜５の直鎖状アルキル基又は一般式（Ｉａ）
【００１６】
【化６】
【００１７】
更に、本発明の一般式（Ｉ）の化合物を製造するための中間体として一般式（ＩＩ）
【００１８】
【化７】
（式中、Ｒは炭素原子数１〜１０の直鎖状アルキル基又は炭素原子数２〜１７の直鎖状アルコキシアルキル基を表わし、Ｊは単結合又は−ＣＨ２ＣＨ２−を表わし、ｍは０又は１の整数を表わし、Ｘ及びＹは各々独立的に、水素原子又はフッ素原子を表わすが、Ｒが炭素原子数１〜１０の直鎖状アルキル基である場合には、Ｘ及びＹのうち、少なくとも一方はフッ素原子を表わし、Ｑは臭素原子又は沃素原子を表わし、シクロヘキサン環はトランス配置を表わす。）で表わされる化合物を提供する。
【００２０】
本発明の一般式（Ｉ）で表わされる化合物は、例えば、次の製造方法に従って製造することができる。
【００２１】
【化８】
（上記中、Ｒ、Ｊ、ｍ、Ｘ、Ｙ、Ｚ及びシクロヘキサン環の配置は一般式（Ｉ）におけると同じ意味を表わし、Ｑ及びＱ’は各々独立的に、沃素原子又は臭素原子を表わす。）
【００２３】
第１段階：一般式（ＩＩ）の化合物を銅とパラジウム等触媒の存在下、２−メチル−３−ブチン−２−オール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段階：一般式（ＩＩＩ）の化合物を水素化ナトリウム等の強塩基と反応させ、一般式（ＩＶ）の化合物を製造する。
第３段階：一般式（ＩＶ）の化合物を銅とパラジウム等触媒の存在下、一般式（Ｖ）の化合物と反応させ、本発明の一般式（Ｉ）の化合物を製造する。
【００２４】
また、本発明の一般式（Ｉ）で表わされる化合物は、次の製造方法に従っても製造することができる。
【００２５】
【化９】
（上記中、Ｒ、Ｊ、ｍ、Ｘ、Ｙ、Ｚ及びシクロヘキサン環の配置は一般式（Ｉ）におけると同じ意味を表わし、Ｑ及びＱ’は各々独立的に、沃素原子又は臭素原子を表わす。）
【００２７】
第１段階：一般式（Ｖ）の化合物を銅とパラジウム等触媒の存在下、２−メチル−３−ブチン−２−オールと反応させることにより、一般式（ＶＩ）の化合物を製造する。
第２段階：一般式（ＶＩ）の化合物を水酸化ナトリウム等の塩基と反応させ、一般式（ＶＩＩ）の化合物を製造する。
第３段階：一般式（ＶＩＩ）の化合物を銅とパラジウム等触媒の存在下、一般式（ＩＩ）の化合物と反応させ、本発明の一般式（Ｉ）の化合物を製造する。
【００２８】
ここで、一般式（ＩＩ）の化合物は、例えば、次の製造方法に従って製造することができる。
【００２９】
【化１０】
（上記中、Ｒ、Ｊ、ｍ、Ｘ、Ｙ及びシクロヘキサン環の配置は一般式（Ｉ）におけると同じ意味を表わし、Ｑ、Ｑ’は前述と同じ意味を表わす。）
【００３１】
第１段階：一般式（ＶＩＩＩ）の化合物をマグネシウムと反応させてグリニャール試剤とした後、一般式（ＩＸ）の化合物と反応させ、一般式（Ｘ）の化合物を製造する。
第２段階：一般式（Ｘ）の化合物を酸触媒の存在下に脱水し、一般式（ＸＩ）の化合物を製造する。
第３段階：一般式（ＸＩ）の化合物をパラジウムカーボン等の触媒の存在下に接触還元した後、塩基の存在下に異性化し、一般式（ＸＩＩ）の化合物を製造する。
第４段階：一般式（ＸＩＩ）の化合物を過沃素酸の存在下、沃素と反応させるか、鉄の存在下、臭素と反応させるか、あるいは、ニトロ化し、還元してアミノ基とした後、ジアゾ分解により、沃素又は臭素化することにより、一般式（ＩＩ）の化合物を製造する。また、特に、Ｘ及びＹが共にフッ素原子である場合には、一般式（ＸＩＩ）の化合物をブチルリチウム等を用いてリチオ化した後、沃素等のハロゲンと反応させることにより、一般式（ＩＩ）の化合物を製造する。
【００３２】
本発明の一般式（Ｉ）で表わされる化合物の優れた特徴は、後述の実施例にも示したが、例えば、以下の例からも明らかである。下記第１表は、現在汎用されている低いしきい値電圧を有する母体液晶（Ａ）８０重量％及び本発明に係わる（Ｎｏ．１）〜（Ｎｏ．６）の化合物各２０重量％からなる各混合液晶について測定した、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を掲示したものである。ただし、（Ｎｏ．７）の化合物については（Ｎｏ．７）の化合物１０重量％及び母体液晶（Ａ）９０重量％からなるものである。また、比較のために母体液晶（Ａ）８０重量％及び式（ａ）の化合物２０重量％、母体液晶（Ａ）８０重量％及び式（ｂ）の化合物２０重量％からなる各混合液晶、更に母体液晶（Ａ）自体についても同様に測定した、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を掲示したものである。
【００３３】
尚、母体液晶（Ａ）は、
【００３４】
【化１１】
からなるものであり、（Ｎｏ．１）〜（Ｎｏ．７）の化合物は、
【００３６】
【化１２】
で表わされるものである。
【００３８】
【表１】
上記第１表から、本発明の（Ｎｏ．１）〜（Ｎｏ．７）の各化合物は、母体液晶のＮ−Ｉ点及びΔｎを上昇させ、しかもしきい値電圧を低下あるいは大きく低下させる効果を有することが明らかである。
【００４０】
これに対して、式（ａ）及び式（ｂ）の化合物は、Ｎ−Ｉ点及びΔｎを大きく上昇させるものの、しきい値電圧を大きく低下させることはできないことが明らかである。
【００４１】
このような違いは、本発明の一般式（Ｉ）の化合物と従来化合物との構造の違い、即ち、本発明の一般式（Ｉ）の化合物は、中央のベンゼン環がフッ素原子によって置換されており、あるいは、シクロヘキサン環側の末端基がアルコキシアルキル基であることにより、誘電率異方性が上昇するとともに、弾性定数が変化しており、これらの相乗効果によって得られるものと考えられる。
【００４２】
本発明の一般式（Ｉ）で表わ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、例えば、４−置換安息香酸４−置換フェニルエステル、４−置換シクロヘキサンカルボン酸４−置換フェニルエステル、４−置換シクロヘキサンカルボン酸４’−置換ビフェニリルエステル、４−（４−置換シクロヘキサンカルボニルオキシ）安息香酸４−置換フェニルエステル、４−（４−置換シクロヘキシル）安息香酸４−置換フェニルエステル、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エステル、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−置換シクロヘキシル）−２−（４−置換フェニル）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）シクロヘキシル］−２−（４−置換フェニル）エチンなどを挙げることができる。
【００４３】
特に、アクティブマトリックス用としては、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、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−置換シクロヘキシル）−２−（４−置換フェニル）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）シクロヘキシル］−２−（４−置換フェニル）エチンなどを挙げることができる。
【００４４】
【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。また、実施例中に使用した化合物 （Ｎｏ．１） 〜 （Ｎｏ．７） の合成方法を （ 合成例 ） として示す。しかしながら、本発明はこれらの実施例に限定されるものではない。
【００４５】
（ 合成例 １） ２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）−１−ヨードベンゼンの合成
（１） １−（３−フルオロフェニル）−４−プロピルシクロヘキセンの合成
【００４６】
【化１３】
マグネシウム３．６ｇをテトラヒドロフラン１０ｍｌに懸濁し、これに３−フルオロ−１−ブロモベンゼン２５．７ｇ（０．１４８モル）のテトラヒドロフラン１２０ｍｌ溶液を、テトラヒドロフランが穏やかに還流を続ける速度で滴下した。滴下終了後、更に１時間室温で攪拌した。この溶液に、４−プロピルシクロヘキサノン１８．７ｇ（０．１３４モル）のテトラヒドロフラン１００ｍｌ溶液を室温で３０分間滴下し、更に室温で１時間攪拌した。反応終了後、反応液が弱酸性になるまで１０％塩酸を加え、反応生成物をトルエン２００ｍｌで抽出した。有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥し、溶媒を溜去した。得られた油状物をトルエン２００ｍｌに溶解し、硫酸水素カリウム３．０ｇを加え、１時間加熱還流させた。室温まで放冷し、飽和炭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、溶媒を溜去して、１−（３−フルオロフェニル）−４−プロピルシクロヘキセン３０．３ｇ（０．１４０モル）を得た。
【００４８】
（２） １−（トランス−４−プロピルシクロヘキシル）−３−フルオロベンゼンの合成
【００４９】
【化１４】
上記（１）で得られた１−（３−フルオロフェニル）−４−プロピルシクロヘキセン３０．３ｇ（０．１４モル）を酢酸エチル３００ｍｌに溶解し、５％パラジウムカーボン３．０ｇを加え、水素圧３気圧で、３時間反応させた。反応終了後、触媒を濾別し、溶媒を溜去した後、Ｎ，Ｎ−ジメチルホルムアミド１５０ｍｌに溶解し、ｔ−ブトキシカリウム３．０ｇを加え、８０℃で４時間攪拌した。水１５０ｍｌを加え、反応生成物をヘキサン１５０ｍｌで抽出し、有機層を水、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。溶媒を溜去し、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）を用いて精製して、１−（トランス−４−プロピルシクロヘキシル）−３−フルオロベンゼン２６．０ｇ（０．１２０モル）を得た。
【００５１】
（３） ２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）−１−ヨードベンゼンの合成
【００５２】
【化１５】
上記（２）で得られた１−（トランス−４−プロピルシクロヘキシル）−３−フルオロベンゼン５．０ｇ（２３ミリモル）を酢酸２５ｍｌに溶解し、これに沃素５．７ｇ、水５ｍｌ、過沃素酸二水和物４．３ｇを加えて３時間加熱還流させた。室温まで放冷し、反応生成物をヘキサン５０ｍｌで抽出した。有機層を１０％亜硫酸ナトリウム水溶液、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、溶媒を溜去した後、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）を用いて精製して、２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）−１−ヨードベンゼン２．６ｇ（７．５ミリモル）を得た。
【００５４】
（合成例 ２） １−（トランス−４−プロピルシクロヘキシル）−３，５−ジフルオロ−４−ヨードベンゼンの合成
（１） １−（３，５−ジフルオロフェニル）−４−プロピルシクロヘキセンの合成
【００５５】
【化１６】
マグネシウム６．９ｇをテトラヒドロフラン１０ｍｌに懸濁し、これに３，５−ジフルオロ−１−ブロモベンゼン５０．０ｇ（０．２５９モル）のテトラヒドロフラン２００ｍｌ溶液を、テトラヒドロフランが穏やかに還流を続ける速度で滴下した。滴下終了後、更に１時間室温で攪拌した。この溶液に、４−プロピルシクロヘキサノン２９．０ｇ（０．２０７モル）のテトラヒドロフラン８０ｍｌ溶液を室温で３０分間滴下し、更に室温で１時間攪拌した。反応終了後、反応液が弱酸性になるまで１０％塩酸を加え、反応生成物をトルエン３００ｍｌで抽出し、有機層を飽和食塩水で洗浄し、無水硫酸ナトリウムで乾燥し、溶媒を溜去した。得られた油状物をトルエン３００ｍｌに溶解し、ｐ−トルエンスルホン酸１水和物２．０ｇを加え、３時間加熱還流させた。室温まで放冷し、飽和炭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、溶媒を溜去して、１−（３，５−ジフルオロフェニル）−４−プロピルシクロヘキセン４８．０ｇ（０．２０３モル）を得た。
【００５７】
（２） １−（トランス−４−プロピルシクロヘキシル）−３，５−ジフルオロベンゼンの合成
【００５８】
【化１７】
上記（１）で得られた１−（３，５−ジフルオロフェニル）−４−プロピルシクロヘキセン４８．６ｇ（０．２０３モル）を酢酸エチル２５０ｍｌに溶解し、５％パラジウムカーボン５ｇを加え、水素圧３気圧で、３時間反応させた。触媒を濾別し、溶媒を溜去した後、Ｎ，Ｎ−ジメチルホルムアミド２５０ｍｌに溶解し、ｔ−ブトキシカリウム２４．３ｇを加え、室温で３時間攪拌した。水２５０ｍｌを加え、反応生成物をヘキサン２００ｍｌで抽出し、有機層を水、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。溶媒を溜去し、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）を用いて精製して、１−（トランス−４−プロピルシクロヘキシル）−３，５−ジフルオロベンゼン３０．２ｇ（０．１２７モル）を得た。
【００６０】
（３） １−（トランス−４−プロピルシクロヘキシル）−３，５−ジフルオロ−４−ヨードベンゼンの合成
【００６１】
【化１８】
上記（２）で得られた１−（トランス−４−プロピルシクロヘキシル）−３，５−ジフルオロベンゼン１４．８ｇ（６２．２ミリモル）をテトラヒドロフラン８０ｍｌに溶解し、−５０℃以下に冷却した。−５０℃以下の温度を保つ速度でｎ−ブチルリチウムヘキサン溶液（１．６８ｍｏｌ／ｌ）４５ｍｌを滴下した。次に、沃素１７．４ｇのテトラヒドロフラン１８０ｍｌ溶液を−５０℃以下の温度を保つ速度で滴下し、更に−５０℃以下で３０分間攪拌した。水５０ｍｌを加えて室温に戻し、反応生成物をヘキサン２００ｍｌで抽出した。有機層を１０％亜硫酸ナトリウム水溶液、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、溶媒を溜去した後、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）を用いて精製して、１−（トランス−４−プロピルシクロヘキシル）−３，５−ジフルオロ−４−ヨードベンゼン２２．０ｇ（６０．４ミリモル）を得た。
【００６３】
（合成例 ３） １−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−ヨードベンゼンの合成
【００６４】
【化１９】
合成例 ２において、４−プロピルシクロヘキサノンに代えて４−（トランス−４−プロピルシクロヘキシル）シクロヘキサノンを用いた以外は合成例 ２と同様にして、１−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−ヨードベンゼンを得た。
【００６６】
（合成例 ４） ４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−１−ヨードベンゼンの合成
合成例 １において、３−フルオロ−１−ブロモベンゼンに代えて、ブロモベンゼンを用い、４−プロピルシクロヘキサノンに代えて４−（３−メトキシプロピル）シクロヘキサノンを用いた以外は合成例 １と同様にして、４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−１−ヨードベンゼンを得た。
【００６７】
（合成例 ５） ２−フルオロ−４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−１−ヨードベンゼンの合成
合成例 １において、４−プロピルシクロヘキサノンに代えて４−（３−メトキシプロピル）シクロヘキサノンを用いた以外は合成例 １と同様にして、２−フルオロ−４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−１−ヨードベンゼンを得た。
【００６８】
（合成例 ６） １−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−３，５−ジフルオロ−４−ヨードベンゼンの合成
合成例 １において、３−フルオロ−１−ブロモベンゼンに代えて、３，５−ジフルオロ−１−ブロモベンゼンを用い、４−プロピルシクロヘキサノンに代えて４−（３−メトキシプロピル）シクロヘキサノンを用いた以外は合成例 １と同様にして、１−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−３，５−ジフルオロ−４−ヨードベンゼンを得た。
【００６９】
（実施例 １） １−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチニル］−３，４，５−トリフルオロベンゼン（Ｎｏ．１の化合物）の合成
（１） ４−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］−２−メチル−３−ブチン−２−オールの合成
【００７０】
【化２０】
合成例 １で得られた２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）−１−ヨードベンゼン７．４０ｇ（１８．８ミリモル）及び２−メチル−３−ブチン−２−オール２．３６ｇ（２５．１ミリモル）をトリエチルアミン３０ｍｌに溶解した。この溶液にヨウ化銅（Ｉ）０．１ｇとジクロロ−ビス（トリフェニルホスフィン）パラジウム（ＩＩ）０．１ｇを加え、１時間室温で攪拌した。反応終了後、水１００ｍｌを加え、反応生成物を酢酸エチル１００ｍｌで抽出し、有機層を水、飽和食塩水で順次洗浄し、更に無水硫酸ナトリウムで乾燥した。溶媒を溜去して、４−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］−２−メチル−３−ブチン−２−オール６．４９ｇ（１８．４ミリモル）を得た。
【００７２】
（２） ２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチンの合成
【００７３】
【化２１】
水素化ナトリウム１ｇをトルエン２０ｍｌに懸濁し、上記（１）で得られた４−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニル］−２−メチル−３−ブチン−２−オール６．４９ｇ（１８．４ミリモル）のトルエン４０ｍｌ溶液を室温で３０分間滴下した。滴下終了後、更に１時間加熱還流させた。室温まで放冷し、水１００ｍｌに加え、有機層を水、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。溶媒を溜去した後、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）を用いて精製して、２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチン２．６０ｇ（１０．７ミリモル）を得た。
【００７５】
（３） １−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチニル］−３，４，５−トリフルオロベンゼンの合成
【００７６】
【化２２】
上記（２）で得た２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチン２．０８ｇ（８．５２ミリモル）及び１−ブロモ−３，４，５−トリフルオロベンゼン１．８０ｇ（８．５３ミリモル）を、トリエチルアミン１０ｍｌ及びジメチルホルムアミド１０ｍｌに溶解した。ヨウ化銅（Ｉ）０．１ｇとジクロロ−ビス（トリフェニルホスフィン）パラジウム（ＩＩ）０．１ｇを加え、３０分間室温で攪拌し、更に１時間加熱還流させた。反応終了後、水１００ｍｌを加え、反応生成物をトルエン１００ｍｌで抽出し、更に有機層を水、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。溶媒を溜去した後、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）を用いて精製して、１−［２−フルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチニル］−３，４，５−トリフルオロベンゼン２．１０ｇ（５．６１ミリモル）を得た。更に、これをエタノールから再結晶させて精製物を得た。この化合物は、７０．５℃で結晶相からネマチック相に、９１．６℃でネマチック相から等方性液体相に相転移した。
【００７８】
（合成例 ７） １−［２，６−ジフルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチニル］−３，４，５−トリフルオロベンゼン（Ｎｏ．２の化合物）の合成
（１） ４−（３，４，５−トリフルオロフェニル）−２−メチル−３−ブチン−２−オールの合成
【００７９】
【化２３】
１−ブロモ−３，４，５−トリフルオロベンゼン３００ｇ（１．４２モル）と２−メチル−３−ブチン−２−オール１４４ｇ（１．７１モル）をＮ，Ｎ−ジメチルホルムアミド９００ｍｌ及びトリエチルアミン３００ｍｌに溶解した。この溶液にヨウ化銅（Ｉ）１．４ｇ及びジクロロ−ビス（トリフェニルホスフィン）パラジウム（ＩＩ）５．０ｇを加え、８０℃で３０分加熱攪拌した。室温まで放冷し、水１．２ｌを加え、反応生成物をヘキサン１．４ｌで抽出し、有機層を水、飽和食塩水で順次洗浄し、更に無水硫酸ナトリウムで乾燥した。溶媒を溜去し、蒸留により精製（ｂ．ｐ．９４〜１００℃／１ｍｍＨｇ）して、４−（３，４，５−トリフルオロフェニル）−２−メチル−３−ブチン−２−オール２７５ｇ（１．２９モル）を得た。
【００８１】
（２） ３，４，５−トリフルオロフェニルエチンの合成
【００８２】
【化２４】
上記（１）で得られた４−（３，４，５−トリフルオロフェニル）−２−メチル−３−ブチン−２−オール５０ｇ（０．２３４モル）に水酸化カリウム０．２３ｇを加えて８０℃で３時間加熱攪拌した。室温まで放冷し、そのまま蒸留により精製（ｂ．ｐ．１３８℃／７６０ｍｍＨｇ）して、３，４，５−トリフルオロフェニルエチン２２．２ｇ（０．１４２モル）を得た。
【００８４】
（３） １−［２，６−ジフルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチニル］−３，４，５−トリフルオロベンゼンの合成
【００８５】
【化２５】
上記（２）で得られた３，４，５−トリフルオロフェニルエチン５．２ｇ（３３．３ミリモル）及び合成例 ２で得られた１−（トランス−４−プロピルシクロヘキシル）−３，５−ジフルオロ−４−ヨードベンゼン１０．０ｇ（２７．５ミリモル）を、トリエチルアミン３０ｍｌ及びジメチルホルムアミド３０ｍｌに溶解した。ヨウ化銅（Ｉ）０．１ｇとジクロロ−ビス（トリフェニルホスフィン）パラジウム（ＩＩ）０．４ｇを加え、３時間加熱還流させた。室温まで放冷した後、水１００ｍｌを加え、反応生成物をトルエン１００ｍｌで抽出し、更に有機層を水、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。溶媒を溜去した後、シリカゲルカラムクロマトグラフィー（展開溶媒：ヘキサン）を用いて精製して、１−［２，６−ジフルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチニル］−３，４，５−トリフルオロベンゼン１０．４ｇ（２６．５ミリモル）を得た。更に、これをエタノールから再結晶させて精製物を得た。この化合物は、９２℃で結晶相からネマチック相に、１０２℃でネマチック相から等方性液体相に相転移した。
【００８７】
（合成例 ８） １−［２，６−ジフルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチニル］−３，５−ジフルオロ−４−トリフルオロメチルベンゼン（Ｎｏ．３の化合物）の合成
【００８８】
【化２６】
合成例 ７において、１−ブロモ−３，４，５−トリフルオロベンゼンに代えて、１−ブロモ−３，５−ジフルオロ−４−トリフルオロメチルベンゼンを用いた以外は合成例 ７と同様にして、１−［２，６−ジフルオロ−４−（トランス−４−プロピルシクロヘキシル）フェニルエチニル］−３，５−ジフルオロ−４−トリフルオロメチルベンゼンを得た。この化合物の融点は８１．０℃であった。
【００９０】
（合成例 ９） １−［４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチニル］−３，４，５−トリフルオロベンゼン（Ｎｏ．４の化合物）の合成
（１） ４−［４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニル］−２−メチル−３−ブチン−２−オールの合成
【００９１】
【化２７】
合成例 ４で得られた４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−１−ヨードベンゼン３０．０ｇ（８３．８ミリモル）と２−メチル−３−ブチン−２−オール１１．０ｇ（１３１ミリモル）をトリエチルアミン９０ｍｌに溶解した。この溶液にヨウ化銅（Ｉ）０．２ｇとジクロロ−ビス（トリフェニルホスフィン）パラジウム（ＩＩ）０．２ｇを加え、１時間室温で攪拌した。反応終了後、水２００ｍｌを加え、反応生成物を酢酸エチル２００ｍｌで抽出し、有機層を水、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。溶媒を溜去し、ヘキサンから再結晶させて精製して、４−［４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニル］−２−メチル−３−ブチン−２−オール２２．１ｇ（７０．４ミリモル）を得た。
【００９３】
（２） ４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチンの合成
【００９４】
【化２８】
水素化ナトリウム１ｇをトルエン２０ｍｌに懸濁し、上記（１）で得た４−［４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニル］−２−メチル−３−ブチン−２−オール２２．１ｇ（７０．４ミリモル）のトルエン２００ｍｌ溶液を、室温で３０分間滴下した。滴下終了後、更に１時間加熱還流させた。室温まで放冷し、水１００ｍｌに加え、有機層を水、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。溶媒を溜去した後、シリカゲルカラムクロマトグラフィー（展開溶媒：トルエン）を用いて精製して、４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチン１３．０ｇ（５０．８ミリモル）を得た。
【００９６】
（３） １−［４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチニル］−３，４，５−トリフルオロベンゼンの合成
【００９７】
【化２９】
上記（２）で得られた４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチン９．４０ｇ（３６．７ミリモル）及び１−ブロモ−３，４，５−トリフルオロベンゼン７．８０ｇ（３７．０ミリモル）を、トリエチルアミン２０ｍｌ及びジメチルホルムアミド５０ｍｌに溶解した。この溶液にヨウ化銅（Ｉ）０．１ｇとジクロロ−ビス）トリフェニルホスフィン）パラジウム（ＩＩ）０．１ｇを加え、３０分間室温で攪拌し、更に１時間加熱還流させた。反応終了後、水１００ｍｌを加え、反応生成物をトルエン１００ｍｌで抽出し、有機層を水、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。溶媒を溜去した後、シリカゲルカラムクロマトグラフィー（展開溶媒：トルエン）を用いて精製して、１−［４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチニル］−３，４，５−トリフルオロベンゼン９．１０ｇ（２３．６ミリモル）を得た。更に、これをメタノールから再結晶させて精製物を得た。この化合物は、６３．５℃で結晶相からネマチック相に、１０８．６℃でネマチック相から等方性液体相に相転移した。
【００９９】
（実施例２） １−［２−フルオロ−４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチニル］−３，５−ジフルオロ−４−トリフルオロメチルベンゼン（Ｎｏ．５の化合物）の合成
【０１００】
【化３０】
合成例 ９において、４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−１−ヨードベンゼンに代えて合成例 ５で得られた２−フルオロ−４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−１−ヨードベンゼンを用い、１−ブロモ−３，４，５−トリフルオロベンゼンに代えて、１−ブロモ−３，５−ジフルオロ−４−トリフルオロメチルベンゼンを用いた以外は合成例 ９と同様にして、１−［２−フルオロ−４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチニル］−３，５−ジフルオロ−４−トリフルオロメチルベンゼンを得た。
【０１０２】
（合成例 １０） １−［２，６−ジフルオロ−４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチニル］−３，４，５−トリフルオロベンゼン（Ｎｏ．６の化合物）の合成
【０１０３】
【化３１】
合成例 ９において、４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−１−ヨードベンゼンに代えて合成例 ６で得られた１−［トランス−４−（３−メトキシプロピル）シクロヘキシル］−３，５−ジフルオロ−４−ヨードベンゼンを用いた以外は合成例 ９と同様にして、１−［２，６−ジフルオロ−４−［トランス−４−（３−メトキシプロピル）シクロヘキシル］フェニルエチニル］−３，４，５−トリフルオロベンゼンを得た。
【０１０５】
（合成例 １１） １−［２，６−ジフルオロ−４−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］フェニルエチニル］−３，４，５−トリフルオロベンゼン（Ｎｏ．７の化合物）の合成
【０１０６】
【化３２】
合成例 ７において、１−（トランス−４−プロピルシクロヘキシル）−３，５−ジフルオロ−４−ヨードベンゼンに代えて、合成例 ３で得られた１−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］−３，５−ジフルオロ−４−ヨードベンゼンを用いた以外は合成例 ７と同様にして、１−［２，６−ジフルオロ−４−［トランス−４−（トランス−４−プロピルシクロヘキシル）シクロヘキシル］フェニルエチニル］−３，４，５−トリフルオロベンゼンを得た。この化合物は、１５５℃で結晶相からネマチック相に相転移し、ネマチック相−等方性液体相転移温度は３００℃以上であった。
【０１０８】
（実施例３） 液晶組成物の調製（１）
【０１０９】
【化３３】
からなる母体液晶（Ａ）を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１１１】
【化３４】
の化合物２０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１１３】
（実施例４） 液晶組成物の調製（２）
実施例３と同様に、母体液晶（Ａ）８０重量％及び合成例 ７の（Ｎｏ．２）
【０１１４】
【化３５】
の化合物２０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１１６】
（実施例５） 液晶組成物の調製（３）
実施例３と同様に、母体液晶（Ａ）８０重量％及び合成例 ８の（Ｎｏ．３）
【０１１７】
【化３６】
の化合物２０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１１９】
（実施例６） 液晶組成物の調製（４）
実施例３と同様に、母体液晶（Ａ）８０重量％及び合成例 ９の（Ｎｏ．４）
【０１２０】
【化３７】
の化合物２０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１２２】
（実施例７） 液晶組成物の調製（５）
実施例３と同様に、母体液晶（Ａ）８０重量％及び実施例２の（Ｎｏ．５）
【０１２３】
【化３８】
の化合物２０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１２５】
（実施例８） 液晶組成物の調製（６）
実施例３と同様に、母体液晶（Ａ）８０重量％及び合成例 １０の（Ｎｏ．６）
【０１２６】
【化３９】
の化合物２０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１２８】
（実施例９） 液晶組成物の調製（７）
実施例３と同様に、母体液晶（Ａ）９０重量％及び合成例 １１の（Ｎｏ．７）
【０１２９】
【化４０】
の化合物１０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１３１】
（比較例１）実施例３と同様に、母体液晶（Ａ）８０重量％及び式（ａ）
【０１３２】
【化４１】
の化合物２０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１３４】
（比較例２）実施例３と同様に、母体液晶（Ａ）８０重量％及び式（ｂ）
【０１３５】
【化４２】
の化合物２０重量％からなる混合液晶を調製し、Ｎ−Ｉ点、２０℃におけるΔｎ及びしきい値電圧を測定したところ、次の通りであった。
【０１３７】
【発明の効果】
本発明の一般式（Ｉ）で表わされる化合物は、ネマチック液晶として現在汎用されている母体液晶との相溶性に優れており、母体液晶のΔｎ、Ｎ−Ｉ点を上昇させ、同時にしきい値電圧を大きく低下させることができる。
【０１３８】
従って、本発明の一般式（Ｉ）で表わされる化合物を用いた液晶組成物は、ワープロ、液晶テレビ等の高速応答性を重視する液晶表示に有用な液晶材料である。[0001]
[Industrial applications]
The present invention relates to a liquid crystal compound which is a novel fluorotolan derivative useful as an electro-optical display material.
[0002]
[Prior art]
The liquid crystal display element is used as an information display element such as a clock, a calculator, and recently, a word processor, a computer terminal display, and the like, and is increasingly important as an interface between an electronic device and a person.
[0003]
Display methods using liquid crystals are roughly classified into three types: (1) a field effect (FEM) type, (2) a dynamic scattering (DSM) type, and (3) a thermal effect (TEM) type. Various display systems have been proposed utilizing these effects, but the display systems using the field effect type have been put to practical use so far. The field effect type is a twisted nematic (TN) type, a super twisted nematic (STN) type, a guest-host (GH) type, an electric field controlled birefringence (ECB) type, a cholesteric-nematic phase transition (CN-PT) type. And a surface stabilized ferroelectric liquid crystal (SSFLC) type. Among them, TN type and STN type are currently the mainstream. Among these, in the STN type, it is possible to increase the capacity to some extent due to improvement of the driving method and the like, but it has reached the limit to recent demand for large display capacity. Therefore, a display method using a non-linear element having a threshold characteristic for each display pixel, for example, an active matrix method such as an MIM (Metal Insulator Metal) method or a TFT (Thin Film Transistor) method using an active element has been put to practical use. , Is rapidly developing toward higher capacity.
[0004]
The liquid crystal materials used in these liquid crystal display systems are required to have various characteristics according to the characteristics of each display system, but can operate in a wide temperature range, can be driven at a low voltage, and Fast response is a common and particularly important requirement. In order to satisfy low-voltage driving, a compound that lowers the threshold voltage when mixed with a liquid crystal composition is required. To enable driving in a wide temperature range, a nematic phase isotropic A compound that raises the ionic liquid phase transition temperature (hereinafter referred to as the NI point) is required.
[0005]
In order to increase the response time, it is necessary to lower the viscosity of the liquid crystal composition. However, the response time can be increased by the following method.
[0006]
In a liquid crystal display TN type cell, if the cell thickness is d (μm) and the response time is τ, there is a proportional relationship between d2 and τ. Can be obtained. However, in order to prevent the occurrence of interference fringes on the cell surface, which may impair the appearance of the cell, the product of the refractive index anisotropy (Δn) of the liquid crystal material filled in the cell and the cell thickness (d) μm ( d.Δn) must be set to a specific value. In a practically used liquid crystal cell, the value of Δn · d is set to 0.5, 1.0, 1.6, or 2.2. Since the value of Δn · d is set to a constant value in this manner, a liquid crystal material having a large value of Δn is required to reduce d and increase the response speed.
[0007]
Also, a liquid crystal material having a large Δn is effective for a polymer-dispersed liquid crystal display element requiring strong white turbidity.
[0008]
Therefore, a compound having a high NI point, a large value of Δn, and capable of lowering the threshold voltage of the composition is very important for preparing a liquid crystal composition satisfying the above requirements. It can be seen, however, that such compounds were largely unknown.
[0009]
As a result of studies based on such points, the present inventors recently found that the NI point is high, the value of Δn is large, and the threshold voltage of the composition can be lowered ( a) and equation (b)
[0010]
Embedded image
Was found. (Japanese Patent Application No. 4-192065) However, the compounds of the above formulas (a) and (b) sufficiently increase the Δn and the NI point when mixed with a currently used base liquid crystal. On the other hand, the threshold voltage was not sufficiently satisfactory, and further improvement was required.
[0012]
[Problems to be solved by the invention]
The problem to be solved by the present invention is to provide a novel compound which, when mixed with a liquid crystal composition, raises the NI point, increases Δn, and effectively lowers the threshold voltage, and It is an object of the present invention to provide a liquid crystal composition containing the compound, and to provide a compound useful as a synthetic intermediate of the compound.
[0013]
[Means for Solving the Problems]
The present invention provides a compound represented by the general formula (I):
[0014]
Embedded image
(Wherein, R represents a linear alkyl group having 1 to 10 carbon atoms or a linear alkoxyalkyl having 2 to 17 carbon atoms, preferably a linear alkyl group having 2 to 5 carbon atoms or a general alkyl group) Formula (Ia)
[0016]
Embedded image
[0017]
Further, as an intermediate for producing the compound of the general formula (I) of the present invention, a compound of the general formula (II)
[0018]
Embedded image
(Wherein, R represents a linear alkyl group having 1 to 10 carbon atoms or a linear alkoxyalkyl group having 2 to 17 carbon atoms, and J represents a single bond or -CH2CH2Represents-, m represents an integer of 0 or 1, X and Y each independently represent a hydrogen atom or a fluorine atom, and when R is a linear alkyl group having 1 to 10 carbon atoms, Represents at least one of X and Y represents a fluorine atom, Q represents a bromine atom or iodine atom, and the cyclohexane ring represents a trans configuration. ) Is provided.
[0020]
The compound represented by the general formula (I) of the present invention can be produced, for example, according to the following production method.
[0021]
Embedded image
(In the above, the arrangement of R, J, m, X, Y, Z and the cyclohexane ring has the same meaning as in the general formula (I), and Q and Q ′ each independently represent an iodine atom or a bromine atom. .)
[0023]
First step: A compound of the general formula (III) is produced by reacting a compound of the general formula (II) with 2-methyl-3-butyn-2-ol in the presence of copper and a catalyst such as palladium.
Second step: reacting the compound of the general formula (III) with a strong base such as sodium hydride to produce a compound of the general formula (IV).
Third step: reacting the compound of the general formula (IV) with the compound of the general formula (V) in the presence of copper and a catalyst such as palladium to produce the compound of the general formula (I) of the present invention.
[0024]
Further, the compound represented by the general formula (I) of the present invention can also be produced according to the following production method.
[0025]
Embedded image
(In the above, the arrangement of R, J, m, X, Y, Z and the cyclohexane ring has the same meaning as in the general formula (I), and Q and Q ′ each independently represent an iodine atom or a bromine atom. .)
[0027]
First step: A compound of the general formula (VI) is produced by reacting a compound of the general formula (V) with 2-methyl-3-butyn-2-ol in the presence of copper and a catalyst such as palladium.
Second step: reacting the compound of the general formula (VI) with a base such as sodium hydroxide to produce a compound of the general formula (VII).
Third step: reacting the compound of the general formula (VII) with the compound of the general formula (II) in the presence of copper and a catalyst such as palladium to produce the compound of the general formula (I) of the present invention.
[0028]
Here, the compound of the general formula (II) can be produced, for example, according to the following production method.
[0029]
Embedded image
(In the above, the arrangement of R, J, m, X, Y and the cyclohexane ring has the same meaning as in the general formula (I), and Q and Q 'have the same meanings as described above.)
[0031]
First step: The compound of the general formula (VIII) is reacted with magnesium to form a Grignard reagent, and then reacted with the compound of the general formula (IX) to produce a compound of the general formula (X).
Second step: The compound of general formula (XI) is dehydrated in the presence of an acid catalyst to produce a compound of general formula (XI).
Third step: The compound of the general formula (XII) is catalytically reduced in the presence of a catalyst such as palladium carbon and then isomerized in the presence of a base to produce a compound of the general formula (XII).
Fourth step: reacting the compound of the general formula (XII) with iodine in the presence of periodic acid, reacting with bromine in the presence of iron, or nitrating and reducing to an amino group; The compound of the general formula (II) is produced by iodine or bromination by diazo decomposition. In particular, when X and Y are both fluorine atoms, the compound of the general formula (XII) is lithiated using butyllithium or the like and then reacted with a halogen such as iodine to obtain the compound represented by the general formula (II) ) Is produced.
[0032]
The excellent characteristics of the compound represented by the general formula (I) of the present invention are shown in Examples described later, and are evident, for example, from the following examples. Table 1 below comprises 80% by weight of a base liquid crystal (A) having a low threshold voltage and 20% by weight of each of the compounds (No. 1) to (No. 6) according to the present invention. It shows the NI point, Δn at 20 ° C., and the threshold voltage measured for each mixed liquid crystal. However, the compound of (No. 7) is composed of 10% by weight of the compound of (No. 7) and 90% by weight of the parent liquid crystal (A). For comparison, each mixed liquid crystal comprising 80% by weight of the base liquid crystal (A) and 20% by weight of the compound of the formula (a), 80% by weight of the base liquid crystal (A) and 20% by weight of the compound of the formula (b), It shows the NI point, Δn at 20 ° C., and the threshold voltage measured in the same manner for the parent liquid crystal (A) itself.
[0033]
The mother liquid crystal (A) is
[0034]
Embedded image
Wherein the compounds of (No. 1) to (No. 7) are:
[0036]
Embedded image
Is represented by
[0038]
[Table 1]
From the above Table 1, the compounds of (No. 1) to (No. 7) of the present invention have the effect of increasing the NI point and Δn of the base liquid crystal, and lowering or greatly lowering the threshold voltage. It is clear that
[0040]
On the other hand, it is clear that the compounds of the formulas (a) and (b) greatly increase the NI point and Δn, but cannot significantly lower the threshold voltage.
[0041]
Such a difference is due to the difference in structure between the compound of the general formula (I) of the present invention and the conventional compound, that is, the compound of the general formula (I) of the present invention has a structure in which the central benzene ring is substituted by a fluorine atom. In addition, since the terminal group on the cyclohexane ring side is an alkoxyalkyl group, the dielectric constant anisotropy increases and the elastic constant changes, which is considered to be obtained by a synergistic effect of these.
[0042]
Preferred representative examples of the nematic liquid crystal compound which can be used as a mixture with the compound represented by formula (I) of the present invention include, for example, 4-substituted benzoic acid 4-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4'-substituted biphenylyl ester, 4- (4-substituted cyclohexanecarbonyloxy) benzoic acid 4-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4- Substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4-substituted cyclohexyl ester, 4,4′-substituted biphenyl, 1- (4-substituted phenyl) -4-substituted cyclohexane, 4,4 ″ -substituted terphenyl , 1- (4′-substituted biphenylyl) -4-substituted cyclohexane, 1- ( -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-substituted cyclohexyl) -2- (4-substituted phenyl) 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) cyclohexyl] -2- (4-substituted phenyl) ethyne and the like can be mentioned.
[0043]
Particularly, for active matrix, 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, 1- (4-substituted cyclohexyl) -2- (4-substituted cyclohexyl) ethane, 1- (4-substituted cyclohexyl) -2- (4-substituted phenyl) 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 cyclohexene) Le) cyclohexyl] -2- (4-substituted phenyl), and the like ethyne.
[0044]
【Example】
Hereinafter, examples of the present invention are shown, and the present invention is further described.Compounds used in Examples (No.1) ~ (No. 7) Synthesis method ( Synthesis example ) Shown asHowever, the invention is not limited to these examples.
[0045]
( Synthesis example 1) Synthesis of 2-fluoro-4- (trans-4-propylcyclohexyl) -1-iodobenzene
(1) Synthesis of 1- (3-fluorophenyl) -4-propylcyclohexene
[0046]
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3.6 g of magnesium was suspended in 10 ml of tetrahydrofuran, and a solution of 25.7 g (0.148 mol) of 3-fluoro-1-bromobenzene in 120 ml of tetrahydrofuran was added dropwise thereto at such a rate that tetrahydrofuran continued to reflux gently. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour. To this solution, a solution of 18.7 g (0.134 mol) of 4-propylcyclohexanone in 100 ml of tetrahydrofuran was added dropwise at room temperature for 30 minutes, and further stirred at room temperature for 1 hour. After completion of the reaction, 10% hydrochloric acid was added until the reaction solution became weakly acidic, and the reaction product was extracted with 200 ml of toluene. The organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off. The obtained oil was dissolved in 200 ml of toluene, 3.0 g of potassium hydrogen sulfate was added, and the mixture was heated under reflux for 1 hour. The mixture was allowed to cool to room temperature, washed sequentially with a saturated aqueous solution of sodium hydrogencarbonate, water and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off to give 1- (3-fluorophenyl) -4-propylcyclohexene 30. 0.3 g (0.140 mol) were obtained.
[0048]
(2) Synthesis of 1- (trans-4-propylcyclohexyl) -3-fluorobenzene
[0049]
Embedded image
30.3 g of 1- (3-fluorophenyl) -4-propylcyclohexene obtained in the above (1) (0.14MoleWas dissolved in 300 ml of ethyl acetate, 3.0 g of 5% palladium carbon was added, and the mixture was reacted at a hydrogen pressure of 3 atm for 3 hours. After completion of the reaction, the catalyst was filtered off and the solvent was distilled off. The residue was dissolved in 150 ml of N, N-dimethylformamide, 3.0 g of potassium t-butoxide was added, and the mixture was stirred at 80 ° C. for 4 hours. 150 ml of water was added, the reaction product was extracted with 150 ml of hexane, and the organic layer was washed successively with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified using silica gel column chromatography (developing solvent: hexane) to obtain 26.0 g (0.120 mol) of 1- (trans-4-propylcyclohexyl) -3-fluorobenzene. .
[0051]
(3) Synthesis of 2-fluoro-4- (trans-4-propylcyclohexyl) -1-iodobenzene
[0052]
Embedded image
5.0 g (23 mmol) of 1- (trans-4-propylcyclohexyl) -3-fluorobenzene obtained in the above (2) was dissolved in 25 ml of acetic acid, and 5.7 g of iodine, 5 ml of water, and periodic acid 4.3 g of dihydrate was added, and the mixture was heated under reflux for 3 hours. After cooling to room temperature, the reaction product was extracted with 50 ml of hexane. The organic layer was washed successively with a 10% aqueous solution of sodium sulfite, water and saturated saline, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified using silica gel column chromatography (developing solvent: hexane). 2.6 g (7.5 mmol) of 2-fluoro-4- (trans-4-propylcyclohexyl) -1-iodobenzene were obtained.
[0054]
(Synthesis example 2) Synthesis of 1- (trans-4-propylcyclohexyl) -3,5-difluoro-4-iodobenzene
(1) Synthesis of 1- (3,5-difluorophenyl) -4-propylcyclohexene
[0055]
Embedded image
6.9 g of magnesium was suspended in 10 ml of tetrahydrofuran, and a solution of 50.0 g (0.259 mol) of 3,5-difluoro-1-bromobenzene in 200 ml of tetrahydrofuran was added dropwise to the suspension at a rate at which tetrahydrofuran continued gentle reflux. After completion of the dropwise addition, the mixture was further stirred at room temperature for 1 hour. To this solution, a solution of 29.0 g (0.207 mol) of 4-propylcyclohexanone in 80 ml of tetrahydrofuran was added dropwise at room temperature for 30 minutes, and further stirred at room temperature for 1 hour. After completion of the reaction, 10% hydrochloric acid was added until the reaction solution became weakly acidic, the reaction product was extracted with 300 ml of toluene, the organic layer was washed with saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off. . The obtained oil was dissolved in 300 ml of toluene, 2.0 g of p-toluenesulfonic acid monohydrate was added, and the mixture was refluxed for 3 hours. The mixture was allowed to cool to room temperature, washed successively with a saturated aqueous solution of sodium hydrogen carbonate, water and saturated saline, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 1- (3,5-difluorophenyl) -4-propyl. 48.0 g (0.203 mol) of cyclohexene were obtained.
[0057]
(2) Synthesis of 1- (trans-4-propylcyclohexyl) -3,5-difluorobenzene
[0058]
Embedded image
48.6 g (0.203 mol) of 1- (3,5-difluorophenyl) -4-propylcyclohexene obtained in the above (1) was dissolved in 250 ml of ethyl acetate, 5 g of 5% palladium carbon was added, and hydrogen pressure was increased. The reaction was performed at 3 atm for 3 hours. After the catalyst was filtered off and the solvent was distilled off, the catalyst was dissolved in 250 ml of N, N-dimethylformamide, 24.3 g of potassium t-butoxide was added, and the mixture was stirred at room temperature for 3 hours. 250 ml of water was added, the reaction product was extracted with 200 ml of hexane, and the organic layer was washed successively with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off, and the residue was purified using silica gel column chromatography (developing solvent: hexane) to give 30.2 g (0.127 mol) of 1- (trans-4-propylcyclohexyl) -3,5-difluorobenzene. Obtained.
[0060]
(3) Synthesis of 1- (trans-4-propylcyclohexyl) -3,5-difluoro-4-iodobenzene
[0061]
Embedded image
14.8 g (62.2 mmol) of 1- (trans-4-propylcyclohexyl) -3,5-difluorobenzene obtained in the above (2) was dissolved in 80 ml of tetrahydrofuran and cooled to −50 ° C. or lower. 45 ml of an n-butyllithium hexane solution (1.68 mol / l) was added dropwise at a rate keeping the temperature at -50 ° C or lower. Next, a solution of 17.4 g of iodine in 180 ml of tetrahydrofuran was added dropwise at a rate keeping the temperature at -50 ° C or lower, and the mixture was further stirred at -50 ° C or lower for 30 minutes. 50 ml of water was added to return to room temperature, and the reaction product was extracted with 200 ml of hexane. The organic layer was washed successively with a 10% aqueous solution of sodium sulfite, water and saturated saline, dried over anhydrous sodium sulfate, the solvent was distilled off, and the residue was purified using silica gel column chromatography (developing solvent: hexane). 22.0 g (60.4 mmol) of 1- (trans-4-propylcyclohexyl) -3,5-difluoro-4-iodobenzene were obtained.
[0063]
(Synthesis example 3) Synthesis of 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-iodobenzene
[0064]
Embedded image
Synthesis example 2Except that 4- (trans-4-propylcyclohexyl) cyclohexanone was used in place of 4-propylcyclohexanoneSynthesis example 21- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-iodobenzene was obtained in the same manner as described above.
[0066]
(Synthesis example 4) Synthesis of 4- [trans-4- (3-methoxypropyl) cyclohexyl] -1-iodobenzene
Synthesis example 1Wherein bromobenzene was used in place of 3-fluoro-1-bromobenzene and 4- (3-methoxypropyl) cyclohexanone was used in place of 4-propylcyclohexanoneSynthesis example 1In the same manner as in the above, 4- [trans-4- (3-methoxypropyl) cyclohexyl] -1-iodobenzene was obtained.
[0067]
(Synthesis example 5) Synthesis of 2-fluoro-4- [trans-4- (3-methoxypropyl) cyclohexyl] -1-iodobenzene
Synthesis example 1Except that 4- (3-methoxypropyl) cyclohexanone was used instead of 4-propylcyclohexanoneSynthesis example 1In the same manner as in the above, 2-fluoro-4- [trans-4- (3-methoxypropyl) cyclohexyl] -1-iodobenzene was obtained.
[0068]
(Synthesis example 6) Synthesis of 1- [trans-4- (3-methoxypropyl) cyclohexyl] -3,5-difluoro-4-iodobenzene
Synthesis example 1Wherein 3,5-difluoro-1-bromobenzene was used in place of 3-fluoro-1-bromobenzene and 4- (3-methoxypropyl) cyclohexanone was used in place of 4-propylcyclohexanoneSynthesis example 11- [trans-4- (3-methoxypropyl) cyclohexyl] -3,5-difluoro-4-iodobenzene was obtained in the same manner as described above.
[0069]
(Example 1) Synthesis of 1- [2-fluoro-4- (trans-4-propylcyclohexyl) phenylethynyl] -3,4,5-trifluorobenzene (Compound No. 1)
(1) Synthesis of 4- [2-fluoro-4- (trans-4-propylcyclohexyl) phenyl] -2-methyl-3-butyn-2-ol
[0070]
Embedded image
Synthesis example 17.40 g (18.8 mmol) of 2-fluoro-4- (trans-4-propylcyclohexyl) -1-iodobenzene and 2.36 g of 2-methyl-3-butyn-2-ol (25. (1 mmol) was dissolved in 30 ml of triethylamine. 0.1 g of copper (I) iodide and 0.1 g of dichloro-bis (triphenylphosphine) palladium (II) were added to this solution, and the mixture was stirred at room temperature for 1 hour. After the completion of the reaction, 100 ml of water was added, the reaction product was extracted with 100 ml of ethyl acetate, and the organic layer was washed with water and saturated saline in this order, and dried over anhydrous sodium sulfate. The solvent was distilled off to obtain 6.49 g (18.4 mmol) of 4- [2-fluoro-4- (trans-4-propylcyclohexyl) phenyl] -2-methyl-3-butyn-2-ol. .
[0072]
(2) Synthesis of 2-fluoro-4- (trans-4-propylcyclohexyl) phenylethyne
[0073]
Embedded image
1 g of sodium hydride is suspended in 20 ml of toluene, and 4- [2-fluoro-4- (trans-4-propylcyclohexyl) phenyl] -2-methyl-3-butyn-2-ol obtained in the above (1) is suspended. A solution of 6.49 g (18.4 mmol) in 40 ml of toluene was added dropwise at room temperature for 30 minutes. After the completion of the dropwise addition, the mixture was further heated under reflux for 1 hour. The mixture was allowed to cool to room temperature, added to 100 ml of water, and the organic layer was washed with water and saturated brine in that order, and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (developing solvent: hexane) to give 2.60 g (10.7 mmol) of 2-fluoro-4- (trans-4-propylcyclohexyl) phenylethyne. Obtained.
[0075]
(3) Synthesis of 1- [2-fluoro-4- (trans-4-propylcyclohexyl) phenylethynyl] -3,4,5-trifluorobenzene
[0076]
Embedded image
2.08 g (8.52 mmol) of 2-fluoro-4- (trans-4-propylcyclohexyl) phenylethyne obtained in the above (2) and 1.80 g of 1-bromo-3,4,5-trifluorobenzene ( 8.53 mmol) was dissolved in 10 ml of triethylamine and 10 ml of dimethylformamide. 0.1 g of copper (I) iodide and 0.1 g of dichloro-bis (triphenylphosphine) palladium (II) were added, the mixture was stirred at room temperature for 30 minutes, and further heated under reflux for 1 hour. After completion of the reaction, 100 ml of water was added, the reaction product was extracted with 100 ml of toluene, and the organic layer was further washed with water and saturated saline in that order, and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was purified by silica gel column chromatography (developing solvent: hexane) to give 1- [2-fluoro-4- (trans-4-propylcyclohexyl) phenylethynyl] -3,4,5. 2.10 g (5.61 mmol) of trifluorobenzene were obtained. Further, this was recrystallized from ethanol to obtain a purified product. This compound underwent a phase transition from a crystalline phase to a nematic phase at 70.5 ° C., and from a nematic phase to an isotropic liquid phase at 91.6 ° C.
[0078]
(Synthesis example 7Synthesis of 1- [2,6-difluoro-4- (trans-4-propylcyclohexyl) phenylethynyl] -3,4,5-trifluorobenzene (compound of No. 2)
(1) Synthesis of 4- (3,4,5-trifluorophenyl) -2-methyl-3-butyn-2-ol
[0079]
Embedded image
300 g (1.42 mol) of 1-bromo-3,4,5-trifluorobenzene and 144 g (1.71 mol) of 2-methyl-3-butyn-2-ol were combined with 900 ml of N, N-dimethylformamide and 300 ml of triethylamine. Was dissolved. To this solution, 1.4 g of copper (I) iodide and 5.0 g of dichloro-bis (triphenylphosphine) palladium (II) were added, followed by heating and stirring at 80 ° C. for 30 minutes. The mixture was allowed to cool to room temperature, 1.2 l of water was added, the reaction product was extracted with 1.4 l of hexane, and the organic layer was washed with water and saturated brine in that order, and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was purified by distillation (bp 94 to 100 ° C / 1 mmHg) to give 275 g of 4- (3,4,5-trifluorophenyl) -2-methyl-3-butyn-2-ol. (1.29 mol).
[0081]
(2) Synthesis of 3,4,5-trifluorophenylethyne
[0082]
Embedded image
0.23 g of potassium hydroxide was added to 50 g (0.234 mol) of 4- (3,4,5-trifluorophenyl) -2-methyl-3-butyn-2-ol obtained in the above (1). The mixture was heated and stirred at 80 ° C for 3 hours. The mixture was allowed to cool to room temperature and purified by distillation (bp 138 ° C / 760 mmHg) as it was to obtain 22.2 g (0.142 mol) of 3,4,5-trifluorophenylethyne.
[0084]
(3) Synthesis of 1- [2,6-difluoro-4- (trans-4-propylcyclohexyl) phenylethynyl] -3,4,5-trifluorobenzene
[0085]
Embedded image
5.2 g (33.3 mmol) of 3,4,5-trifluorophenylethyne obtained in the above (2) andSynthesis example 21- (trans-4-propylcyclohexyl) -3,5-difluoro-4-iodobenzene 10.0 g (27.5 mmol) obtained in was dissolved in 30 ml of triethylamine and 30 ml of dimethylformamide. 0.1 g of copper (I) iodide and 0.4 g of dichloro-bis (triphenylphosphine) palladium (II) were added, and the mixture was heated under reflux for 3 hours. After cooling to room temperature, 100 ml of water was added, the reaction product was extracted with 100 ml of toluene, and the organic layer was further washed with water and saturated saline in that order, and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue is purified by silica gel column chromatography (developing solvent: hexane) to give 1- [2,6-difluoro-4- (trans-4-propylcyclohexyl) phenylethynyl] -3,4. 10.4 g (26.5 mmol) of 5,5-trifluorobenzene were obtained. Further, this was recrystallized from ethanol to obtain a purified product. The compound underwent a phase transition from a crystalline phase to a nematic phase at 92 ° C. and a phase transition from a nematic phase to an isotropic liquid phase at 102 ° C.
[0087]
(Synthesis example 8Synthesis of 1- [2,6-difluoro-4- (trans-4-propylcyclohexyl) phenylethynyl] -3,5-difluoro-4-trifluoromethylbenzene (compound of No. 3)
[0088]
Embedded image
Synthesis example 7Except that 1-bromo-3,5-difluoro-4-trifluoromethylbenzene was used instead of 1-bromo-3,4,5-trifluorobenzeneSynthesis example 7In the same manner as in the above, 1- [2,6-difluoro-4- (trans-4-propylcyclohexyl) phenylethynyl] -3,5-difluoro-4-trifluoromethylbenzene was obtained. The melting point of this compound was 81.0 ° C.
[0090]
(Synthesis example 9) Synthesis of 1- [4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethynyl] -3,4,5-trifluorobenzene (Compound No. 4)
(1) Synthesis of 4- [4- [trans-4- (3-methoxypropyl) cyclohexyl] phenyl] -2-methyl-3-butyn-2-ol
[0091]
Embedded image
Synthesis example 430.0 g (83.8 mmol) of 4- [trans-4- (3-methoxypropyl) cyclohexyl] -1-iodobenzene and 11.0 g of 2-methyl-3-butyn-2-ol (131) Mmol) was dissolved in 90 ml of triethylamine. To this solution, 0.2 g of copper (I) iodide and 0.2 g of dichloro-bis (triphenylphosphine) palladium (II) were added, followed by stirring at room temperature for 1 hour. After completion of the reaction, 200 ml of water was added, the reaction product was extracted with 200 ml of ethyl acetate, and the organic layer was sequentially washed with water and saturated saline, and dried over anhydrous sodium sulfate. The solvent was distilled off and the residue was purified by recrystallization from hexane to give 4- [4- [trans-4- (3-methoxypropyl) cyclohexyl] phenyl] -2-methyl-3-butyn-2-ol. 1 g (70.4 mmol) were obtained.
[0093]
(2) Synthesis of 4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethyne
[0094]
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1 g of sodium hydride is suspended in 20 ml of toluene, and 4- [4- [trans-4- (3-methoxypropyl) cyclohexyl] phenyl] -2-methyl-3-butyn-2-ol obtained in the above (1) is suspended. A solution of 22.1 g (70.4 mmol) in 200 ml of toluene was added dropwise at room temperature for 30 minutes. After the completion of the dropwise addition, the mixture was further heated under reflux for 1 hour. The mixture was allowed to cool to room temperature, added to 100 ml of water, and the organic layer was washed with water and saturated brine in that order, and dried over anhydrous sodium sulfate. After distilling off the solvent, the residue was purified using silica gel column chromatography (developing solvent: toluene) to obtain 13.0 g (50.8 mmol) of 4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethyne. Got.
[0096]
(3) Synthesis of 1- [4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethynyl] -3,4,5-trifluorobenzene
[0097]
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9.40 g (36.7 mmol) of 4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethyne obtained in (2) above and 1-bromo-3,4,5-trifluorobenzene 7. 80 g (37.0 mmol) were dissolved in 20 ml of triethylamine and 50 ml of dimethylformamide. To this solution, 0.1 g of copper (I) iodide and 0.1 g of dichloro-bis) triphenylphosphine) palladium (II) were added, and the mixture was stirred at room temperature for 30 minutes, and further heated under reflux for 1 hour. After completion of the reaction, 100 ml of water was added, the reaction product was extracted with 100 ml of toluene, and the organic layer was sequentially washed with water and saturated saline, and dried over anhydrous sodium sulfate. After evaporating the solvent, the residue was purified using silica gel column chromatography (developing solvent: toluene) to give 1- [4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethynyl] -3,4,4. 9.10 g (23.6 mmol) of 5-trifluorobenzene were obtained. Further, this was recrystallized from methanol to obtain a purified product. This compound underwent a phase transition from a crystalline phase to a nematic phase at 63.5 ° C., and from a nematic phase to an isotropic liquid phase at 108.6 ° C.
[0099]
(Example2Synthesis of 1- [2-fluoro-4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethynyl] -3,5-difluoro-4-trifluoromethylbenzene (compound of No. 5)
[0100]
Embedded image
Synthesis example 9Wherein, instead of 4- [trans-4- (3-methoxypropyl) cyclohexyl] -1-iodobenzene,Synthesis example 5Using 2-fluoro-4- [trans-4- (3-methoxypropyl) cyclohexyl] -1-iodobenzene obtained in the above in place of 1-bromo-3,4,5-trifluorobenzene. Except that bromo-3,5-difluoro-4-trifluoromethylbenzene was used.Synthesis example 9In the same manner as in the above, 1- [2-fluoro-4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethynyl] -3,5-difluoro-4-trifluoromethylbenzene was obtained.
[0102]
(Synthesis example 10) Synthesis of 1- [2,6-difluoro-4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethynyl] -3,4,5-trifluorobenzene (Compound No. 6)
[0103]
Embedded image
Synthesis example 9Wherein, instead of 4- [trans-4- (3-methoxypropyl) cyclohexyl] -1-iodobenzene,Synthesis example 6Except that the 1- [trans-4- (3-methoxypropyl) cyclohexyl] -3,5-difluoro-4-iodobenzene obtained in the above was used.Synthesis example 91- [2,6-Difluoro-4- [trans-4- (3-methoxypropyl) cyclohexyl] phenylethynyl] -3,4,5-trifluorobenzene was obtained in the same manner as described above.
[0105]
(Synthesis example 11Synthesis of 1- [2,6-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] phenylethynyl] -3,4,5-trifluorobenzene (compound of No. 7)
[0106]
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Synthesis example 7Wherein 1- (trans-4-propylcyclohexyl) -3,5−Instead of difluoro-4-iodobenzene,Synthesis example 3Except that the 1- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] -3,5-difluoro-4-iodobenzene obtained in the above was used.Synthesis example 7In the same manner as in the above, 1- [2,6-difluoro-4- [trans-4- (trans-4-propylcyclohexyl) cyclohexyl] phenylethynyl] -3,4,5-trifluorobenzene was obtained. This compound underwent a phase transition from a crystalline phase to a nematic phase at 155 ° C., and the nematic phase-isotropic liquid phase transition temperature was 300 ° C. or higher.
[0108]
(Example3) Preparation of liquid crystal composition (1)
[0109]
Embedded image
Was prepared and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0111]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0113]
(Example4) Preparation of liquid crystal composition (2)
Example3Similarly to the above, 80% by weight of the base liquid crystal (A) andSynthesis example 7(No. 2)
[0114]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0116]
(Example5) Preparation of liquid crystal composition (3)
Example3Similarly to the above, 80% by weight of the base liquid crystal (A) andSynthesis example 8(No.3)
[0117]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0119]
(Example6) Preparation of liquid crystal composition (4)
Example3Similarly to the above, 80% by weight of the base liquid crystal (A) andSynthesis example 9(No. 4)
[0120]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0122]
(Example7) Preparation of liquid crystal composition (5)
Example380% by weight of the base liquid crystal (A) and2(No. 5)
[0123]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0125]
(Example8) Preparation of liquid crystal composition (6)
Example3Similarly to the above, 80% by weight of the base liquid crystal (A) andSynthesis example 10(No. 6)
[0126]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0128]
(Example9) Preparation of liquid crystal composition (7)
Example390% by weight of the base liquid crystal (A) andSynthesis example 11(No. 7)
[0129]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0131]
(Comparative Example 1) Example3Similarly to the above, 80% by weight of the base liquid crystal (A) and the formula (a)
[0132]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0134]
(Comparative Example 2) Example3Similarly to the above, 80% by weight of the base liquid crystal (A) and the formula (b)
[0135]
Embedded image
Was prepared, and the NI point, Δn at 20 ° C. and the threshold voltage were measured. The results were as follows.
[0137]
【The invention's effect】
The compound represented by the general formula (I) of the present invention has excellent compatibility with a base liquid crystal which is currently widely used as a nematic liquid crystal, increases the Δn and the NI point of the base liquid crystal, and simultaneously increases the threshold value. The voltage can be greatly reduced.
[0138]
Therefore, the liquid crystal composition using the compound represented by the general formula (I) of the present invention is a useful liquid crystal material for a liquid crystal display, such as a word processor or a liquid crystal television, which emphasizes high-speed response.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29976293A JP3569935B2 (en) | 1993-01-28 | 1993-11-30 | Fluorotran derivative |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1253693 | 1993-01-28 | ||
| JP5-12536 | 1993-01-28 | ||
| JP29976293A JP3569935B2 (en) | 1993-01-28 | 1993-11-30 | Fluorotran derivative |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06279332A JPH06279332A (en) | 1994-10-04 |
| JP3569935B2 true JP3569935B2 (en) | 2004-09-29 |
Family
ID=26348165
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29976293A Expired - Lifetime JP3569935B2 (en) | 1993-01-28 | 1993-11-30 | Fluorotran derivative |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3569935B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103429705A (en) * | 2011-03-24 | 2013-12-04 | 默克专利股份有限公司 | Compounds having a C-C-triple bond |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP7255131B2 (en) * | 2018-10-23 | 2023-04-11 | Dic株式会社 | liquid crystal compound |
-
1993
- 1993-11-30 JP JP29976293A patent/JP3569935B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103429705A (en) * | 2011-03-24 | 2013-12-04 | 默克专利股份有限公司 | Compounds having a C-C-triple bond |
| US9777217B2 (en) | 2011-03-24 | 2017-10-03 | Merck Patent Gmbh | Compounds having a C—C triple bond |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06279332A (en) | 1994-10-04 |
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