JPH06263663A - Fluorine-containing indane ring derivative compound and liquid crystal composition containing the compound - Google Patents
Fluorine-containing indane ring derivative compound and liquid crystal composition containing the compoundInfo
- Publication number
- JPH06263663A JPH06263663A JP5076218A JP7621893A JPH06263663A JP H06263663 A JPH06263663 A JP H06263663A JP 5076218 A JP5076218 A JP 5076218A JP 7621893 A JP7621893 A JP 7621893A JP H06263663 A JPH06263663 A JP H06263663A
- Authority
- JP
- Japan
- Prior art keywords
- group
- compound
- liquid crystal
- added
- fluorine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 58
- -1 indane ring derivative compound Chemical class 0.000 title claims abstract description 47
- 239000000203 mixture Substances 0.000 title claims description 50
- 229910052731 fluorine Inorganic materials 0.000 title claims description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims description 9
- 239000011737 fluorine Substances 0.000 title claims description 9
- 150000001875 compounds Chemical class 0.000 title abstract description 86
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 18
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 14
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 claims abstract description 7
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 125000001153 fluoro group Chemical group F* 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 4
- 125000004434 sulfur atom Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 3
- 125000005708 carbonyloxy group Chemical group [*:2]OC([*:1])=O 0.000 claims description 3
- 125000005740 oxycarbonyl group Chemical group [*:1]OC([*:2])=O 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 125000004122 cyclic group Chemical group 0.000 claims 2
- 125000004955 1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])C([H])([*:1])C([H])([H])C([H])([H])C1([H])[*:2] 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052749 magnesium Inorganic materials 0.000 abstract description 6
- 125000005407 trans-1,4-cyclohexylene group Chemical group [H]C1([H])C([H])([H])[C@]([H])([*:2])C([H])([H])C([H])([H])[C@@]1([H])[*:1] 0.000 abstract description 6
- 229910052740 iodine Inorganic materials 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- 229910052794 bromium Inorganic materials 0.000 abstract description 3
- GSBJCTWVCYTIBQ-UHFFFAOYSA-N 5,6-difluoro-2-(4-propylphenyl)-2,3-dihydro-1h-indene Chemical compound C1=CC(CCC)=CC=C1C1CC2=CC(F)=C(F)C=C2C1 GSBJCTWVCYTIBQ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052801 chlorine Inorganic materials 0.000 abstract description 2
- 229910052736 halogen Inorganic materials 0.000 abstract description 2
- 150000002367 halogens Chemical class 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 abstract 1
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- 150000002468 indanes Chemical class 0.000 abstract 1
- 229910000765 intermetallic Inorganic materials 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 46
- 239000000126 substance Substances 0.000 description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 30
- 239000012044 organic layer Substances 0.000 description 29
- 239000002904 solvent Substances 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 24
- 238000004458 analytical method Methods 0.000 description 23
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- 238000001816 cooling Methods 0.000 description 19
- 239000010410 layer Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000000463 material Substances 0.000 description 13
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 11
- 238000004440 column chromatography Methods 0.000 description 10
- 238000010992 reflux Methods 0.000 description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 210000002858 crystal cell Anatomy 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- CYNYIHKIEHGYOZ-UHFFFAOYSA-N 1-bromopropane Chemical compound CCCBr CYNYIHKIEHGYOZ-UHFFFAOYSA-N 0.000 description 5
- ZRWCHMFGMKNWEC-UHFFFAOYSA-N 1-iodo-4-propylbenzene Chemical compound CCCC1=CC=C(I)C=C1 ZRWCHMFGMKNWEC-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 235000019441 ethanol Nutrition 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- FPOCXYWEBBMGFD-UHFFFAOYSA-N 5,6-difluoro-1,3-dihydroinden-2-one Chemical compound C1=C(F)C(F)=CC2=C1CC(=O)C2 FPOCXYWEBBMGFD-UHFFFAOYSA-N 0.000 description 4
- UMKXMUVPBIIAFC-UHFFFAOYSA-N 5,6-difluoro-1h-indene Chemical compound C1=C(F)C(F)=CC2=C1C[CH][CH]2 UMKXMUVPBIIAFC-UHFFFAOYSA-N 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- XMJZWRSJWRRBDH-KYZUINATSA-N CCC[C@H](CC1)CC[C@@H]1Cl Chemical compound CCC[C@H](CC1)CC[C@@H]1Cl XMJZWRSJWRRBDH-KYZUINATSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 4
- GVNVAWHJIKLAGL-UHFFFAOYSA-N 2-(cyclohexen-1-yl)cyclohexan-1-one Chemical compound O=C1CCCCC1C1=CCCCC1 GVNVAWHJIKLAGL-UHFFFAOYSA-N 0.000 description 3
- OSJRTWXVMCRBKZ-UHFFFAOYSA-N 5,6-difluoro-2,3-dihydroinden-1-one Chemical compound C1=C(F)C(F)=CC2=C1C(=O)CC2 OSJRTWXVMCRBKZ-UHFFFAOYSA-N 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 101150065749 Churc1 gene Proteins 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 102100038239 Protein Churchill Human genes 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 230000020169 heat generation Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000003392 indanyl group Chemical group C1(CCC2=CC=CC=C12)* 0.000 description 3
- 125000005647 linker group Chemical group 0.000 description 3
- 150000002736 metal compounds Chemical class 0.000 description 3
- 238000010898 silica gel chromatography Methods 0.000 description 3
- LTMRRSWNXVJMBA-UHFFFAOYSA-L 2,2-diethylpropanedioate Chemical compound CCC(CC)(C([O-])=O)C([O-])=O LTMRRSWNXVJMBA-UHFFFAOYSA-L 0.000 description 2
- AOOGDRDMPQCKGJ-UHFFFAOYSA-N 3,3-difluoro-1,2-dihydroindene Chemical compound C1=CC=C2C(F)(F)CCC2=C1 AOOGDRDMPQCKGJ-UHFFFAOYSA-N 0.000 description 2
- JPHKMYXKNKLNDF-UHFFFAOYSA-N 3,4-difluorobenzaldehyde Chemical compound FC1=CC=C(C=O)C=C1F JPHKMYXKNKLNDF-UHFFFAOYSA-N 0.000 description 2
- UOZIYCHJMUNLIG-UHFFFAOYSA-N 3-(3,4-difluorophenyl)propanoic acid Chemical compound OC(=O)CCC1=CC=C(F)C(F)=C1 UOZIYCHJMUNLIG-UHFFFAOYSA-N 0.000 description 2
- DDDFLVOQZPSQPV-UHFFFAOYSA-N 3-(3,4-difluorophenyl)propanoyl chloride Chemical compound FC1=CC=C(CCC(Cl)=O)C=C1F DDDFLVOQZPSQPV-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- VGOZNIPJKGIMBZ-UHFFFAOYSA-N 5,6-dimethyl-1,3-dihydroinden-2-one Chemical compound C1=C(C)C(C)=CC2=C1CC(=O)C2 VGOZNIPJKGIMBZ-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- YRGOPJGSKKUYQP-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1CC2=CC(=C(C=C2C1)F)F Chemical compound BrC1=CC=C(C=C1)C1CC2=CC(=C(C=C2C1)F)F YRGOPJGSKKUYQP-UHFFFAOYSA-N 0.000 description 2
- BORLGESDMKBTEL-UHFFFAOYSA-N C(CC)C1=CC=C(C=C1)C#CC1CC2=CC(=C(C=C2C1)F)F Chemical compound C(CC)C1=CC=C(C=C1)C#CC1CC2=CC(=C(C=C2C1)F)F BORLGESDMKBTEL-UHFFFAOYSA-N 0.000 description 2
- NJMCLDUSBJSLNV-UHFFFAOYSA-N C(CC)C1=CC=C(C=C1)C1(CC2=CC(=C(C=C2C1)F)F)O Chemical compound C(CC)C1=CC=C(C=C1)C1(CC2=CC(=C(C=C2C1)F)F)O NJMCLDUSBJSLNV-UHFFFAOYSA-N 0.000 description 2
- WIHAQXWBQNIZJG-UHFFFAOYSA-N C1C2=CC(=C(C=C2C=C1C(=O)O)F)F Chemical compound C1C2=CC(=C(C=C2C=C1C(=O)O)F)F WIHAQXWBQNIZJG-UHFFFAOYSA-N 0.000 description 2
- YHCAWMOIJQWWFK-UHFFFAOYSA-N CCOC(=O)C(=CC1=CC(=C(C=C1)F)F)C(=O)OCC Chemical compound CCOC(=O)C(=CC1=CC(=C(C=C1)F)F)C(=O)OCC YHCAWMOIJQWWFK-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- NQRYJNQNLNOLGT-UHFFFAOYSA-N Piperidine Chemical compound C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 229910006404 SnO 2 Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- SUVZQBFPIPPBOB-UHFFFAOYSA-N diethyl 2-[(3,4-difluorophenyl)methyl]propanedioate Chemical compound CCOC(=O)C(C(=O)OCC)CC1=CC=C(F)C(F)=C1 SUVZQBFPIPPBOB-UHFFFAOYSA-N 0.000 description 2
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000005262 ferroelectric liquid crystals (FLCs) Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 2
- 229910003446 platinum oxide Inorganic materials 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000003566 sealing material Substances 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- MYIUBTXFTRVRLQ-UHFFFAOYSA-N (5,6-difluoro-2,3-dihydro-1h-inden-2-yl)methanol Chemical compound FC1=C(F)C=C2CC(CO)CC2=C1 MYIUBTXFTRVRLQ-UHFFFAOYSA-N 0.000 description 1
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-Bis(diphenylphosphino)propane Substances C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 1
- SWJPEBQEEAHIGZ-UHFFFAOYSA-N 1,4-dibromobenzene Chemical compound BrC1=CC=C(Br)C=C1 SWJPEBQEEAHIGZ-UHFFFAOYSA-N 0.000 description 1
- NENLTGZCBUWVGN-UHFFFAOYSA-N 1-(2-bromoethyl)-4-propylbenzene Chemical compound CCCC1=CC=C(CCBr)C=C1 NENLTGZCBUWVGN-UHFFFAOYSA-N 0.000 description 1
- ICPVFOAWQNIBBW-UHFFFAOYSA-N 1-(bromomethyl)-4-propylbenzene Chemical compound CCCC1=CC=C(CBr)C=C1 ICPVFOAWQNIBBW-UHFFFAOYSA-N 0.000 description 1
- YBYIRNPNPLQARY-UHFFFAOYSA-N 1H-indene Natural products C1=CC=C2CC=CC2=C1 YBYIRNPNPLQARY-UHFFFAOYSA-N 0.000 description 1
- FONLDTYQLFYTOM-UHFFFAOYSA-N 2,3-dihydro-1h-indene-2-carbonyl chloride Chemical compound C1=CC=C2CC(C(=O)Cl)CC2=C1 FONLDTYQLFYTOM-UHFFFAOYSA-N 0.000 description 1
- 125000005714 2,5- (1,3-dioxanylene) group Chemical group [H]C1([H])OC([H])([*:1])OC([H])([H])C1([H])[*:2] 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- IIXBKFFEZMDAOS-UHFFFAOYSA-N 2-bromo-5-propylpyrimidine Chemical compound CCCC1=CN=C(Br)N=C1 IIXBKFFEZMDAOS-UHFFFAOYSA-N 0.000 description 1
- LCHYEKKJCUJAKN-UHFFFAOYSA-N 2-propylphenol Chemical compound CCCC1=CC=CC=C1O LCHYEKKJCUJAKN-UHFFFAOYSA-N 0.000 description 1
- GICIECWTEWJCRE-UHFFFAOYSA-N 3,4,4,7-tetramethyl-2,3-dihydro-1h-naphthalene Chemical group CC1=CC=C2C(C)(C)C(C)CCC2=C1 GICIECWTEWJCRE-UHFFFAOYSA-N 0.000 description 1
- KLSLBUSXWBJMEC-UHFFFAOYSA-N 4-Propylphenol Chemical compound CCCC1=CC=C(O)C=C1 KLSLBUSXWBJMEC-UHFFFAOYSA-N 0.000 description 1
- NVXOOHIRSARTSR-UHFFFAOYSA-N 5,6-difluoro-2,3-dihydro-1h-indene Chemical compound C1=C(F)C(F)=CC2=C1CCC2 NVXOOHIRSARTSR-UHFFFAOYSA-N 0.000 description 1
- RMTMLFPARWFPQS-UHFFFAOYSA-N 5,6-difluoro-2,3-dihydro-1h-indene-2-carboxylic acid Chemical compound FC1=C(F)C=C2CC(C(=O)O)CC2=C1 RMTMLFPARWFPQS-UHFFFAOYSA-N 0.000 description 1
- GLOPJSKPLKCGSS-UHFFFAOYSA-N BrC1=CC=C(C=C1)C1(CC2=CC(=C(C=C2C1)F)F)O Chemical compound BrC1=CC=C(C=C1)C1(CC2=CC(=C(C=C2C1)F)F)O GLOPJSKPLKCGSS-UHFFFAOYSA-N 0.000 description 1
- NCPSSJQDSHUGMW-UHFFFAOYSA-N C(CC)C1=CC=C(C=C1)C(C(F)(F)C1CC2=CC(=C(C=C2C1)F)F)(F)F Chemical compound C(CC)C1=CC=C(C=C1)C(C(F)(F)C1CC2=CC(=C(C=C2C1)F)F)(F)F NCPSSJQDSHUGMW-UHFFFAOYSA-N 0.000 description 1
- DSERINPGOSQWEA-UHFFFAOYSA-N C(CC)C1=CC=C(CCC2CC3=CC(=C(C=C3C2)F)F)C=C1 Chemical compound C(CC)C1=CC=C(CCC2CC3=CC(=C(C=C3C2)F)F)C=C1 DSERINPGOSQWEA-UHFFFAOYSA-N 0.000 description 1
- TYSFXLCBHGEGDZ-UHFFFAOYSA-N C(CC)C1CC2=CC(=C(C=C2C1)F)F Chemical compound C(CC)C1CC2=CC(=C(C=C2C1)F)F TYSFXLCBHGEGDZ-UHFFFAOYSA-N 0.000 description 1
- AEQWZCIQKSUUSL-NNUKFRKNSA-N C(CC)[C@@H]1CC[C@H](CC1)C1(CC2=CC(=C(C=C2C1)F)F)O Chemical compound C(CC)[C@@H]1CC[C@H](CC1)C1(CC2=CC(=C(C=C2C1)F)F)O AEQWZCIQKSUUSL-NNUKFRKNSA-N 0.000 description 1
- TVTILKHSDWHTES-QAQDUYKDSA-N C(CC)[C@@H]1CC[C@H](CC1)C1=CC=C(C=C1)C1CC2=CC(=C(C=C2C1)F)F Chemical compound C(CC)[C@@H]1CC[C@H](CC1)C1=CC=C(C=C1)C1CC2=CC(=C(C=C2C1)F)F TVTILKHSDWHTES-QAQDUYKDSA-N 0.000 description 1
- WVGWWVPVHVBGIN-UHFFFAOYSA-N C1C(CC2=CC(=C(C=C21)F)F)Cl Chemical compound C1C(CC2=CC(=C(C=C21)F)F)Cl WVGWWVPVHVBGIN-UHFFFAOYSA-N 0.000 description 1
- REUPJFPKZAXGFR-KTSLABGISA-N C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](Cl)CC1 Chemical compound C1C[C@@H](CCC)CC[C@@H]1[C@@H]1CC[C@@H](Cl)CC1 REUPJFPKZAXGFR-KTSLABGISA-N 0.000 description 1
- DJWGJGUWQGPGIQ-UHFFFAOYSA-N CCCC1=CC=C(C=C1)C(C(C2CC3=CC(=C(C=C3C2)F)F)Br)Br Chemical compound CCCC1=CC=C(C=C1)C(C(C2CC3=CC(=C(C=C3C2)F)F)Br)Br DJWGJGUWQGPGIQ-UHFFFAOYSA-N 0.000 description 1
- ONXRZRSWJNEDIC-UHFFFAOYSA-N CCCC1=CC=C(C=C1)CC(=O)C2CC3=CC(=C(C=C3C2)F)F Chemical compound CCCC1=CC=C(C=C1)CC(=O)C2CC3=CC(=C(C=C3C2)F)F ONXRZRSWJNEDIC-UHFFFAOYSA-N 0.000 description 1
- ABDSHEXJIRBSCA-UHFFFAOYSA-N CCCC1OCC(CO1)Br Chemical group CCCC1OCC(CO1)Br ABDSHEXJIRBSCA-UHFFFAOYSA-N 0.000 description 1
- ZXSLJDQNFFDFAJ-VVPTUSLJSA-N CCC[C@H](CC1)CC[C@@H]1[C@H](CC1)CC[C@@H]1C(CC1=C2)=CC1=CC(F)=C2F Chemical compound CCC[C@H](CC1)CC[C@@H]1[C@H](CC1)CC[C@@H]1C(CC1=C2)=CC1=CC(F)=C2F ZXSLJDQNFFDFAJ-VVPTUSLJSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCNJAXROONQCHG-UHFFFAOYSA-N ClC=1CC2=CC(=C(C=C2C1)F)F Chemical compound ClC=1CC2=CC(=C(C=C2C1)F)F YCNJAXROONQCHG-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- OWMXFSYAFMVWNN-YPKPFQOOSA-N F\C(=C(/[Si](C)(C)C)\F)\C1CC2=CC(=C(C=C2C1)F)F Chemical group F\C(=C(/[Si](C)(C)C)\F)\C1CC2=CC(=C(C=C2C1)F)F OWMXFSYAFMVWNN-YPKPFQOOSA-N 0.000 description 1
- XMGCTBPALOQBGL-VZUCSPMQSA-N F\C(=C\F)\C1CC2=CC(=C(C=C2C1)F)F Chemical group F\C(=C\F)\C1CC2=CC(=C(C=C2C1)F)F XMGCTBPALOQBGL-VZUCSPMQSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- PUHYIRXLFUDSHC-UHFFFAOYSA-N [Li]C1CC2=CC(=C(C=C2C1)F)F Chemical compound [Li]C1CC2=CC(=C(C=C2C1)F)F PUHYIRXLFUDSHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000002252 acyl group Chemical group 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 1
- QNXSIUBBGPHDDE-UHFFFAOYSA-N alpha-indanone Natural products C1=CC=C2C(=O)CCC2=C1 QNXSIUBBGPHDDE-UHFFFAOYSA-N 0.000 description 1
- 125000005337 azoxy group Chemical group [N+]([O-])(=N*)* 0.000 description 1
- PQNFLJBBNBOBRQ-UHFFFAOYSA-N benzocyclopentane Natural products C1=CC=C2CCCC2=C1 PQNFLJBBNBOBRQ-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- XAEWZDYWZHIUCT-UHFFFAOYSA-N desipramine hydrochloride Chemical group [H+].[Cl-].C1CC2=CC=CC=C2N(CCCNC)C2=CC=CC=C21 XAEWZDYWZHIUCT-UHFFFAOYSA-N 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 125000000532 dioxanyl group Chemical group 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000004313 glare Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002469 indenes Chemical class 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- PDJAZCSYYQODQF-UHFFFAOYSA-N iodine monofluoride Chemical compound IF PDJAZCSYYQODQF-UHFFFAOYSA-N 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- UHZYTMXLRWXGPK-UHFFFAOYSA-N phosphorus pentachloride Chemical compound ClP(Cl)(Cl)(Cl)Cl UHZYTMXLRWXGPK-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 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
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000001256 steam distillation Methods 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Liquid Crystal Substances (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
Abstract
Description
【0001】[0001]
【産業上の利用分野】本発明は、含フッ素インダン誘導
体化合物およびそれを含有する液晶組成物に関する。TECHNICAL FIELD The present invention relates to a fluorine-containing indane derivative compound and a liquid crystal composition containing the compound.
【0002】[0002]
【従来の技術】液晶表示素子は、時計、電卓をはじめ、
近年では測定器、自動車用計器、複写器、カメラ、OA
機器用表示装置、家電製品用表示装置等種々の用途に使
用され始めており、広い動作温度範囲、低動作電圧、高
速応答性、高コントラスト比、広視角、化学的安定性等
の種々の性能要求がなされている。2. Description of the Related Art Liquid crystal display devices include clocks, calculators,
In recent years, measuring instruments, automobile instruments, copying machines, cameras, OA
It has begun to be used in various applications such as device display devices and home appliance display devices, and various performance requirements such as wide operating temperature range, low operating voltage, high-speed response, high contrast ratio, wide viewing angle, chemical stability, etc. Has been done.
【0003】しかし、現在のところ、これらの特性を単
独の材料ですべて満たす材料はなく、複数の液晶、およ
び非液晶の材料を混合して液晶組成物として要求性能を
満たしている状態である。このため、各種特性のすべて
ではなく、一または二以上の特性に優れた液晶または非
液晶の材料開発が望まれている。However, at present, there is no material satisfying all of these characteristics with a single material, and a plurality of liquid crystal and non-liquid crystal materials are mixed to satisfy the required performance as a liquid crystal composition. For this reason, it is desired to develop a liquid crystal or non-liquid crystal material that is excellent in one or two or more of all the characteristics.
【0004】[0004]
【発明が解決しようとする課題】液晶を用いた表示素子
分野においては、その性能向上が望まれており、低電圧
駆動、高精細表示、高コントラスト比、広視角特性、低
温応答特性、広動作温度範囲等が望まれており、これら
はいずれかを向上させると他のいずれかが犠牲になると
いう傾向がある。In the field of display devices using liquid crystals, it is desired to improve their performance, and low voltage driving, high definition display, high contrast ratio, wide viewing angle characteristics, low temperature response characteristics, wide operation are required. Temperature ranges and the like are desired, and any one of them tends to be sacrificed when the other is improved.
【0005】特に、最近は低電圧駆動と高速応答が望ま
れている。このためには、いくつかの改善方法が考えら
れるが、その一つとして誘電率異方性が大きく、低粘性
の液晶組成物の採用がある。このような目的のため、一
般的には末端にシアノ基を導入した誘電率異方性の大き
な液晶材料が提案されている。Particularly, recently, low voltage driving and high speed response are desired. For this purpose, some improvement methods can be considered. One of them is to adopt a liquid crystal composition having a large dielectric anisotropy and a low viscosity. For this purpose, a liquid crystal material having a large dielectric anisotropy in which a cyano group is introduced at the terminal is generally proposed.
【0006】しかし、シアノ基のように強い極性基を持
った化合物は、一般にイオン性の不純物を溶かしやす
く、解離させやすいため、電荷保持率が高温やUV照射
によって低下してしまうという欠点があった。また、そ
の添加によってバルク粘度も大きくなってしまう。そこ
で最近、フッ素の導入による低粘性で高電荷保持率の材
料が開発されているが、シアノ基を持つ液晶材料に比べ
ると、誘電率異方性は小さい。However, a compound having a strong polar group such as a cyano group generally has a drawback that the ionic impurities are easily dissolved and easily dissociated, so that the charge retention rate is lowered by high temperature or UV irradiation. It was Moreover, the bulk viscosity also becomes large by the addition. Therefore, recently, a material having a low viscosity and a high charge retention rate by introducing fluorine has been developed, but the dielectric anisotropy is smaller than that of a liquid crystal material having a cyano group.
【0007】したがって、低粘性で高電荷保持率、高誘
電率異方性を持つ液晶材料が望まれていた。Therefore, a liquid crystal material having low viscosity, high charge retention and high dielectric anisotropy has been desired.
【0008】[0008]
【課題を解決するための手段】本発明は、前述の課題を
解決すべく、新規な材料を提供するものであり、下記一
般式(1) で表される含フッ素インダン環誘導体化合物を
提供する。The present invention provides a novel material to solve the above-mentioned problems, and provides a fluorine-containing indane ring derivative compound represented by the following general formula (1): .
【0009】R-(A1)m-Y1-(A2)n-Y2-In(F) (1)R- (A 1 ) m -Y 1- (A 2 ) n -Y 2 -In (F) (1)
【0010】ただし、一般式(1) 中、A1、A2、Y1、Y2、
R 、m 、n は下記のものを示す。A1、A2は相互に独立し
てトランス-1,4- シクロヘキシレン基、1-シクロヘキセ
ン−1,4-イレン基および1,4-フェニレン基から選ばれる
環基であり、これらの環基は夫々非置換であるかあるい
は置換基として1個以上のハロゲン原子、シアノ基を有
し、これらの環基中環を構成する1個以上の=CH-基は窒
素原子に置換されていてもよく、また、環を構成する1
個以上の-CH2- 基は酸素原子もしくは硫黄原子に置換さ
れていてもよい。However, in the general formula (1), A 1 , A 2 , Y 1 , Y 2 ,
R, m and n are as follows. A 1 and A 2 are each independently a ring group selected from a trans-1,4-cyclohexylene group, a 1-cyclohexene-1,4-ylene group and a 1,4-phenylene group. Are each unsubstituted or have at least one halogen atom or cyano group as a substituent, and at least group constituting the ring in these ring groups may be substituted with a nitrogen atom. , Also forming a ring 1
One or more —CH 2 — groups may be substituted with oxygen atoms or sulfur atoms.
【0011】Y1、Y2は相互に独立して-COO- 、 -OCO-、
-C≡C-、-CH2CH2-、-CH=CH- 、-OCH2-、-CH2O-、-CF2CF
2-、-CF=CF- または単結合を示す。Y 1 and Y 2 are independently of each other -COO-, -OCO-,
-C≡C-, -CH 2 CH 2- , -CH = CH-, -OCH 2- , -CH 2 O-, -CF 2 CF
2- , -CF = CF- or indicates a single bond.
【0012】R は炭素数 1〜10のアルキル基、ハロゲン
原子あるいはシアノ基を示し、アルキル基の場合には、
このアルキル基中の炭素−炭素結合間あるいはこのアル
キル基と環基との間の炭素−炭素結合間に酸素原子、カ
ルボニルオキシ基、あるいはオキシカルボニル基が挿入
されてもよく、また、そのアルキル基中の炭素−炭素結
合の一部が三重結合あるいは二重結合に置換されていて
もよく、また、そのアルキル基内の1個の-CH2- 基がカ
ルボニル基に置換されていてもよく、また、そのアルキ
ル基中の水素原子の一部もしくはすべてがフッ素原子に
置換されていてもよい。R represents an alkyl group having 1 to 10 carbon atoms, a halogen atom or a cyano group, and in the case of an alkyl group,
An oxygen atom, a carbonyloxy group, or an oxycarbonyl group may be inserted between the carbon-carbon bond in the alkyl group or between the carbon-carbon bond between the alkyl group and the ring group. Part of the carbon-carbon bond in the may be replaced with a triple bond or a double bond, and one -CH 2- group in the alkyl group may be replaced with a carbonyl group, Further, some or all of the hydrogen atoms in the alkyl group may be replaced with fluorine atoms.
【0013】m 、n は相互に独立して 0または 1を示
す。また、-In(F)は、5,6-ジフルオロインダン-2- イル
基を示す。M and n each independently represent 0 or 1. In addition, -In (F) represents a 5,6-difluoroindan-2-yl group.
【0014】また、一般式 (2) R-In(F)(式中、R につ
いては、一般式 (1)のものと同じものを示す)で表され
ることを特徴とする含フッ素インダン環誘導体化合物、
および、一般式(1) または一般式(2) で示される化合物
を含有することを特徴とする液晶組成物、および、一般
式(1) または一般式(2) で示される化合物を電極付基板
間に挟持してなる液晶電気光学素子を提供する。Further, a fluorine-containing indane ring characterized by being represented by the general formula (2) R-In (F) (wherein R represents the same as that of the general formula (1)) Derivative compounds,
And a liquid crystal composition containing a compound represented by the general formula (1) or the general formula (2), and a substrate with an electrode containing the compound represented by the general formula (1) or the general formula (2) A liquid crystal electro-optical element sandwiched therebetween is provided.
【0015】本発明の一般式(1) の化合物は、低粘性で
あり、高電荷保持率および大きな誘電率異方性を持ち、
かつ、他の液晶または非液晶との相溶性に優れ、化学的
にも安定な材料である。The compound of the general formula (1) of the present invention has low viscosity, high charge retention and large dielectric anisotropy,
In addition, it is a chemically stable material with excellent compatibility with other liquid crystals or non-liquid crystals.
【0016】本発明の化合物の具体的構造としては、以
下のような化合物がある。なお、以下の説明において
は、一般式(3) の化合物に限らず、「-In(F)」は、5,6-
ジフルオロインダン-2- イル基を表し、「-Ph-」は1,4-
フェニレン基を表し、「-Cy-」はトランス-1,4- シクロ
ヘキシレン基を表し、「-Ch-」は1-シクロヘキセン-1,4
- イレン基を表す。なお、1-シクロヘキセン-1,4- イレ
ン基においては2つの異性体が存在するが、本発明にお
いては、そのどちらでもよく、また、その混合物でもよ
い。 R-In(F) (3)Specific structures of the compounds of the present invention include the following compounds. In the following description, not only the compound of the general formula (3) but also "-In (F)" means 5,6-
Represents a difluoroindan-2-yl group, and "-Ph-" is 1,4-
Represents a phenylene group, "-Cy-" represents a trans-1,4-cyclohexylene group, "-Ch-" represents 1-cyclohexene-1,4
-Represents an iren group. Although there are two isomers in the 1-cyclohexene-1,4-ylene group, in the present invention, either one may be present, or a mixture thereof may be used. R-In (F) (3)
【0017】[0017]
【化1】 [Chemical 1]
【0018】また、1,4-フェニレン基を1つ有する化合
物としては、具体的には以下のような化合物がある。 R-Ph-In(F) (4A)Specific examples of the compound having one 1,4-phenylene group include the following compounds. R-Ph-In (F) (4A)
【0019】[0019]
【化2】 [Chemical 2]
【0020】R-Ph-OCO-In(F) (4B) R-Ph-COO-In(F) (4C) R-Ph-C ≡C-In(F) (4D) R-Ph-CH2CH2-In(F) (4E) R-Ph-CH=CH-In(F) (4F) R-Ph-CH2O-In(F) (4G) R-Ph-OCH2-In(F) (4H) R-Ph-CF2CF2-In(F) (4I) R-Ph-CF=CF-In(F) (4J)R-Ph-OCO-In (F) (4B) R-Ph-COO-In (F) (4C) R-Ph-C ≡ C-In (F) (4D) R-Ph-CH 2 CH 2 -In (F) (4E) R-Ph-CH = CH-In (F) (4F) R-Ph-CH 2 O-In (F) (4G) R-Ph-OCH 2 -In (F ) (4H) R-Ph-CF 2 CF 2 -In (F) (4I) R-Ph-CF = CF-In (F) (4J)
【0021】また、1-シクロヘキセン-1,4- イレン基を
1つ有する化合物としては、具体的には以下のような化
合物がある。 R-Ch-In(F) (5A)Specific examples of the compound having one 1-cyclohexene-1,4-ylene group include the following compounds. R-Ch-In (F) (5A)
【0022】[0022]
【化3】 [Chemical 3]
【0023】R-Ch-OCO-In(F) (5B) R-Ch-COO-In(F) (5C) R-Ch-C ≡C-In(F) (5D) R-Ch-CH2CH2-In(F) (5E) R-Ch-CH=CH-In(F) (5F) R-Ch-CH2O-In(F) (5G) R-Ch-OCH2-In(F) (5H) R-Ch-CF2CF2-In(F) (5I) R-Ch-CF=CF-In(F) (5J)R-Ch-OCO-In (F) (5B) R-Ch-COO-In (F) (5C) R-Ch-C ≡ C-In (F) (5D) R-Ch-CH 2 CH 2 -In (F) (5E) R-Ch-CH = CH-In (F) (5F) R-Ch-CH 2 O-In (F) (5G) R-Ch-OCH 2 -In (F ) (5H) R-Ch-CF 2 CF 2 -In (F) (5I) R-Ch-CF = CF-In (F) (5J)
【0024】また、トランス-1,4- シクロヘキシレン基
を1つ有する化合物としては、具体的には以下のような
化合物がある。 R-Cy-In(F) (6A)Specific examples of the compound having one trans-1,4-cyclohexylene group are as follows. R-Cy-In (F) (6A)
【0025】[0025]
【化4】 [Chemical 4]
【0026】R-Cy-OCO-In(F) (6B) R-Cy-COO-In(F) (6C) R-Cy-C ≡C-In(F) (6D) R-Cy-CH2CH2-In(F) (6E) R-Cy-CH=CH-In(F) (6F) R-Cy-CH2O-In(F) (6G) R-Cy-OCH2-In(F) (6H) R-Cy-CF2CF2-In(F) (6I) R-Cy-CF=CF-In(F) (6J)R-Cy-OCO-In (F) (6B) R-Cy-COO-In (F) (6C) R-Cy-C ≡C-In (F) (6D) R-Cy-CH 2 CH 2 -In (F) (6E) R-Cy-CH = CH-In (F) (6F) R-Cy-CH 2 O-In (F) (6G) R-Cy-OCH 2 -In (F ) (6H) R-Cy-CF 2 CF 2 -In (F) (6I) R-Cy-CF = CF-In (F) (6J)
【0027】また、インダン環基以外に環基を2つ有す
る化合物としては、具体的には以下のような化合物があ
る。Specific examples of the compound having two ring groups other than the indane ring group include the following compounds.
【0028】R-Ph-Ph-In(F) (7A) R-Ph-Ph-OCO-In(F) (7B) R-Ph-Ph-COO-In(F) (7C) R-Ph-Ph-C≡C-In(F) (7D) R-Ph-Ph-CH2CH2-In(F) (7E) R-Ph-Ph-CH=CH-In(F) (7F) R-Ph-Ph-CH2O-In(F) (7G) R-Ph-Ph-OCH2-In(F) (7H) R-Ph-Ph-CF2CF2-In(F) (7I) R-Ph-Ph-CF=CF-In(F) (7J)R-Ph-Ph-In (F) (7A) R-Ph-Ph-OCO-In (F) (7B) R-Ph-Ph-COO-In (F) (7C) R-Ph- Ph-C≡C-In (F) (7D) R-Ph-Ph-CH 2 CH 2 -In (F) (7E) R-Ph-Ph-CH = CH-In (F) (7F) R- Ph-Ph-CH 2 O-In (F) (7G) R-Ph-Ph-OCH 2 -In (F) (7H) R-Ph-Ph-CF 2 CF 2 -In (F) (7I) R -Ph-Ph-CF = CF-In (F) (7J)
【0029】R-Ch-Ch-In(F) (8A) R-Ch-Ch-OCO-In(F) (8B) R-Ch-Ch-COO-In(F) (8C) R-Ch-Ch-C≡C-In(F) (8D) R-Ch-Ch-CH2CH2-In(F) (8E) R-Ch-Ch-CH=CH-In(F) (8F) R-Ch-Ch-CH2O-In(F) (8G) R-Ch-Ch-OCH2-In(F) (8H) R-Ch-Ch-CF2CF2-In(F) (8I) R-Ch-Ch-CF=CF-In(F) (8J)R-Ch-Ch-In (F) (8A) R-Ch-Ch-OCO-In (F) (8B) R-Ch-Ch-COO-In (F) (8C) R-Ch- Ch-C≡C-In (F) (8D) R-Ch-Ch-CH 2 CH 2 -In (F) (8E) R-Ch-Ch-CH = CH-In (F) (8F) R- Ch-Ch-CH 2 O-In (F) (8G) R-Ch-Ch-OCH 2 -In (F) (8H) R-Ch-Ch-CF 2 CF 2 -In (F) (8I) R -Ch-Ch-CF = CF-In (F) (8J)
【0030】R-Cy-Cy-In(F) (9A) R-Cy-Cy-OCO-In(F) (9B) R-Cy-Cy-COO-In(F) (9C) R-Cy-Cy-C≡C-In(F) (9D) R-Cy-Cy-CH2CH2-In(F) (9E) R-Cy-Cy-CH=CH-In(F) (9F) R-Cy-Cy-CH2O-In(F) (9G) R-Cy-Cy-OCH2-In(F) (9H) R-Cy-Cy-CF2CF2-In(F) (9I) R-Cy-Cy-CF=CF-In(F) (9J)R-Cy-Cy-In (F) (9A) R-Cy-Cy-OCO-In (F) (9B) R-Cy-Cy-COO-In (F) (9C) R-Cy- Cy-C≡C-In (F) (9D) R-Cy-Cy-CH 2 CH 2 -In (F) (9E) R-Cy-Cy-CH = CH-In (F) (9F) R- Cy-Cy-CH 2 O-In (F) (9G) R-Cy-Cy-OCH 2 -In (F) (9H) R-Cy-Cy-CF 2 CF 2 -In (F) (9I) R -Cy-Cy-CF = CF-In (F) (9J)
【0031】R-Ch-Ph-In(F) (10A) R-Ch-Ph-OCO-In(F) (10B) R-Ch-Ph-COO-In(F) (10C) R-Ch-Ph-C≡C-In(F) (10D) R-Ch-Ph-CH2CH2-In(F) (10E) R-Ch-Ph-CH=CH-In(F) (10F) R-Ch-Ph-CH2O-In(F) (10G) R-Ch-Ph-OCH2-In(F) (10H) R-Ch-Ph-CF2CF2-In(F) (10I) R-Ch-Ph-CF=CF-In(F) (10J)R-Ch-Ph-In (F) (10A) R-Ch-Ph-OCO-In (F) (10B) R-Ch-Ph-COO-In (F) (10C) R-Ch- Ph-C≡C-In (F) (10D) R-Ch-Ph-CH 2 CH 2 -In (F) (10E) R-Ch-Ph-CH = CH-In (F) (10F) R- Ch-Ph-CH 2 O-In (F) (10G) R-Ch-Ph-OCH 2 -In (F) (10H) R-Ch-Ph-CF 2 CF 2 -In (F) (10I) R -Ch-Ph-CF = CF-In (F) (10J)
【0032】R-Cy-Ph-In(F) (11A) R-Cy-Ph-OCO-In(F) (11B) R-Cy-Ph-COO-In(F) (11C) R-Cy-Ph-C≡C-In(F) (11D) R-Cy-Ph-CH2CH2-In(F) (11E) R-Cy-Ph-CH=CH-In(F) (11F) R-Cy-Ph-CH2O-In(F) (11G) R-Cy-Ph-OCH2-In(F) (11H) R-Cy-Ph-CF2CF2-In(F) (11I) R-Cy-Ph-CF=CF-In(F) (11J)R-Cy-Ph-In (F) (11A) R-Cy-Ph-OCO-In (F) (11B) R-Cy-Ph-COO-In (F) (11C) R-Cy- Ph-C≡C-In (F) (11D) R-Cy-Ph-CH 2 CH 2 -In (F) (11E) R-Cy-Ph-CH = CH-In (F) (11F) R- Cy-Ph-CH 2 O-In (F) (11G) R-Cy-Ph-OCH 2 -In (F) (11H) R-Cy-Ph-CF 2 CF 2 -In (F) (11I) R -Cy-Ph-CF = CF-In (F) (11J)
【0033】R-Cy-Ch-In(F) (12A) R-Cy-Ch-OCO-In(F) (12B) R-Cy-Ch-COO-In(F) (12C) R-Cy-Ch-C≡C-In(F) (12D) R-Cy-Ch-CH2CH2-In(F) (12E) R-Cy-Ch-CH=CH-In(F) (12F) R-Cy-Ch-CH2O-In(F) (12G) R-Cy-Ch-OCH2-In(F) (12H) R-Cy-Ch-CF2CF2-In(F) (12I) R-Cy-Ch-CF=CF-In(F) (12J)R-Cy-Ch-In (F) (12A) R-Cy-Ch-OCO-In (F) (12B) R-Cy-Ch-COO-In (F) (12C) R-Cy- Ch-C≡C-In (F) (12D) R-Cy-Ch-CH 2 CH 2 -In (F) (12E) R-Cy-Ch-CH = CH-In (F) (12F) R- Cy-Ch-CH 2 O-In (F) (12G) R-Cy-Ch-OCH 2 -In (F) (12H) R-Cy-Ch-CF 2 CF 2 -In (F) (12I) R -Cy-Ch-CF = CF-In (F) (12J)
【0034】R-Ch-Cy-In(F) (13A) R-Ch-Cy-OCO-In(F) (13B) R-Ch-Cy-COO-In(F) (13C) R-Ch-Cy-C≡C-In(F) (13D) R-Ch-Cy-CH2CH2-In(F) (13E) R-Ch-Cy-CH=CH-In(F) (13F) R-Ch-Cy-CH2O-In(F) (13G) R-Ch-Cy-OCH2-In(F) (13H) R-Ch-Cy-CF2CF2-In(F) (13I) R-Ch-Cy-CF=CF-In(F) (13J)R-Ch-Cy-In (F) (13A) R-Ch-Cy-OCO-In (F) (13B) R-Ch-Cy-COO-In (F) (13C) R-Ch- Cy-C≡C-In (F) (13D) R-Ch-Cy-CH 2 CH 2 -In (F) (13E) R-Ch-Cy-CH = CH-In (F) (13F) R- Ch-Cy-CH 2 O-In (F) (13G) R-Ch-Cy-OCH 2 -In (F) (13H) R-Ch-Cy-CF 2 CF 2 -In (F) (13I) R -Ch-Cy-CF = CF-In (F) (13J)
【0035】また、1,4-フェニレン基の一部の水素原子
がフッ素原子に置換されたフェニレン基を有する化合物
としては、以下のような化合物がある。なお、「PhF」 は
モノフルオロ−1,4-フェニレン基あるいはポリフルオロ
−1,4-フェニレン基を表す。ただし、iは1〜4の整数
を表す。 R-PhF-In(F) (14)Further, as a compound having a phenylene group in which some hydrogen atoms of the 1,4-phenylene group are replaced by fluorine atoms, there are the following compounds. In addition, "PhF" represents a monofluoro-1,4-phenylene group or a polyfluoro-1,4-phenylene group. However, i represents the integer of 1-4. R-PhF-In (F) (14)
【0036】[0036]
【化5】 [Chemical 5]
【0037】このほか、インダン環基以外に環基を2つ
有する化合物の場合において、環と環との間の結合基を
単結合以外の結合基に変更した化合物として、以下のよ
うな化合物もある。In addition, in the case of a compound having two ring groups in addition to the indane ring group, the following compounds may be used as a compound in which the bonding group between the rings is changed to a bonding group other than a single bond. is there.
【0038】R-Ph-OCO-Ph-In(F) (7K) R-Ph-COO-Ph-In(F) (7L) R-Ph-C ≡C-Ph-In(F) (7M) R-Ph-CH2CH2-Ph-In(F) (7N) R-Ph-CH=CH-Ph-In(F) (7O) R-Ph-CH2O-Ph-In(F) (7P) R-Ph-OCH2-Ph-In(F) (7Q) R-Ph-CF2CF2-Ph-In(F) (7R) R-Ph-CF=CF-Ph-In(F) (7S)R-Ph-OCO-Ph-In (F) (7K) R-Ph-COO-Ph-In (F) (7L) R-Ph-C ≡ C-Ph-In (F) (7M) R-Ph-CH 2 CH 2 -Ph-In (F) (7N) R-Ph-CH = CH-Ph-In (F) (7O) R-Ph-CH 2 O-Ph-In (F) ( 7P) R-Ph-OCH 2 -Ph-In (F) (7Q) R-Ph-CF 2 CF 2 -Ph-In (F) (7R) R-Ph-CF = CF-Ph-In (F) (7S)
【0039】また、一般式(1) におけるA2の1,4-フェニ
レン基、トランス-1,4- シクロヘキシレン基、1-シクロ
ヘキセン-1,4- イレン基の水素原子の一部をハロゲン原
子またはシアノ基に置換したり、環を構成する=CH-基の
一部を窒素原子にしたり、または、環を構成する-CH2-
基の一部を酸素原子または硫黄原子に置換した例として
以下のような化合物が挙げられる。In addition, a part of the hydrogen atoms of the 1,4-phenylene group, trans-1,4-cyclohexylene group and 1-cyclohexene-1,4-ylene group of A 2 in the general formula (1) is a halogen atom. Alternatively, a cyano group may be substituted, a ring-forming = CH- group may be partly replaced by a nitrogen atom, or a ring-forming -CH 2-
The following compounds may be mentioned as examples in which a part of the groups is replaced with an oxygen atom or a sulfur atom.
【0040】[0040]
【化6】 [Chemical 6]
【0041】本発明の一般式(1) の化合物は、その少な
くとも1種を他の液晶材料および/または非液晶材料と
混合して液晶組成物として使用される。それにより、そ
の液晶組成物を低粘性かつ誘電率異方性を大きくするこ
とができ、液晶表示素子とした場合に低電圧駆動および
高速応答が可能になる。The compound of the general formula (1) of the present invention is used as a liquid crystal composition by mixing at least one of them with other liquid crystal material and / or non-liquid crystal material. Thereby, the liquid crystal composition can have low viscosity and large dielectric anisotropy, and when it is used as a liquid crystal display device, low voltage driving and high speed response are possible.
【0042】本発明の化合物と混合させる物質として
は、例えば以下のようなものがある。なお、以下の式で
のRC、RDはアルキル基、アルコキシ基、ハロゲン原子、
シアノ基等の基を表す。ただし、「-NON-」 はアゾキシ基
を表す。Examples of the substance to be mixed with the compound of the present invention are as follows. In the formulas below, R C and R D are an alkyl group, an alkoxy group, a halogen atom,
Represents a group such as a cyano group. However, "-NON-" represents an azoxy group.
【0043】RC-Cy-Cy-RD RC-Cy-Ph-RD RC-Ph-Ph-RD R C -Cy-Cy-R D R C -Cy-Ph-R D R C -Ph-Ph-R D
【0044】RC-Cy-COO-Ph-RD RC-Ph-COO-Ph-RD RC-Cy-CH=CH-Ph-RD RC-Ph-CH=CH-Ph-RD RC-Cy-CH2CH2-Ph-RD RC-Ph-CH2CH2-Ph-RD RC-Ph-N=N-Ph-RD RC-Ph-NON-Ph-RD RC-Cy-COS-Ph-RD R C -Cy-COO-Ph-R D R C -Ph-COO-Ph-R D R C -Cy-CH = CH-Ph-R D R C -Ph-CH = CH-Ph-R D R C -Cy-CH 2 CH 2 -Ph-R D R C -Ph-CH 2 CH 2 -Ph-R D R C -Ph-N = N-Ph-R D R C -Ph-NON-Ph -R D R C -Cy-COS-Ph-R D
【0045】RC-Cy-Ph-Ph-RD RC-Cy-Ph-Ph-Cy-RD RC-Ph-Ph-Ph-RD RC-Cy-COO-Ph-Ph-RD RC-Cy-Ph-COO-Ph-RD RC-Cy-COO-Ph-COO-Ph-RD RC-Ph-COO-Ph-COO-Ph-RD RC-Ph-COO-Ph-OCO-Ph-RD R C -Cy-Ph-Ph-R D R C -Cy-Ph-Ph-Cy-R D R C -Ph-Ph-Ph-R D R C -Cy-COO-Ph-Ph-R D R C -Cy-Ph-COO-Ph-R D R C -Cy-COO-Ph-COO-Ph-R D R C -Ph-COO-Ph-COO-Ph-R D R C -Ph-COO -Ph-OCO-Ph-R D
【0046】[0046]
【化7】 [Chemical 7]
【0047】なお、これらの化合物は単なる例示にすぎ
なく、環構造もしくは末端基の水素原子をハロゲン原
子、シアノ基、メチル基等に置換してもよく、また、シ
クロヘキサン環、ベンゼン環を他の六員環、五員環、例
えば、ピリジン環、ジオキサン環等に置換してもよく、
さらに、環と環の間の結合基を変更することも可能であ
り、所望の性能に合わせて種々の材料が選択使用されれ
ばよい。These compounds are merely examples, and the hydrogen atom of the ring structure or the terminal group may be replaced with a halogen atom, a cyano group, a methyl group, etc., and the cyclohexane ring and the benzene ring may be replaced with other compounds. A 6-membered ring, a 5-membered ring, for example, a pyridine ring, a dioxane ring and the like may be substituted,
Further, it is possible to change the bonding group between the rings, and various materials may be selected and used according to the desired performance.
【0048】本発明の化合物を含む液晶組成物は、液晶
セルに注入する等して、電極付の基板間に挟持され、液
晶電気光学素子を構成する。代表的な液晶セルとして
は、ツイストネマチック(TN)型液晶電気光学素子が
ある。なお、ここで液晶電気光学素子と表現しているの
は、表示用途以外、例えば、調光窓、光シャッター、偏
光交換素子等にも使用できることを明らかにしているた
めである。The liquid crystal composition containing the compound of the present invention is sandwiched between substrates with electrodes by injection into a liquid crystal cell or the like to form a liquid crystal electro-optical element. A typical liquid crystal cell is a twisted nematic (TN) type liquid crystal electro-optical element. The expression "liquid crystal electro-optical element" is used here because it is clarified that the liquid crystal electro-optical element can be used for a light control window, an optical shutter, a polarization exchange element, etc., in addition to the display application.
【0049】上記液晶電気光学素子は、TN方式、ゲス
トホスト(GH)方式、動的散乱方式、フェーズチェン
ジ方式、DAP方式、二周波駆動方式、強誘電性液晶表
示方式等種々のモードで使用することができる。The liquid crystal electro-optical element is used in various modes such as a TN system, a guest host (GH) system, a dynamic scattering system, a phase change system, a DAP system, a dual frequency drive system and a ferroelectric liquid crystal display system. be able to.
【0050】以下に、液晶電気光学素子の構成および製
法の具体例を示す。プラスチック、ガラス等の基板上
に、必要に応じてSiO2、Al2O3 等のアンダーコート層や
カラーフィルター層を形成し、In2O3-SnO2(ITO)、
SnO2等の電極を設け、パターニングした後、必要に応じ
てポリイミド、ポリアミド、SiO2、Al2O3 等のオーバー
コート層を形成し、配向処理し、これにシール材を印刷
し、電極面が相対向するように配して周辺をシールし、
シール材を硬化して空セルを形成する。Specific examples of the structure and manufacturing method of the liquid crystal electro-optical element will be shown below. If necessary, an undercoat layer such as SiO 2 or Al 2 O 3 or a color filter layer may be formed on a substrate such as plastic or glass, and In 2 O 3 -SnO 2 (ITO),
After providing an electrode such as SnO 2 and patterning, if necessary, form an overcoat layer of polyimide, polyamide, SiO 2 , Al 2 O 3, etc., perform orientation treatment, print a sealing material on this, and print the electrode surface Are arranged so that they face each other, and the periphery is sealed,
The sealing material is cured to form an empty cell.
【0051】この空セルに、本発明の化合物を含む組成
物を注入し、注入口を封止剤で封止して液晶セルを構成
する。この液晶セルに必要に応じて偏光板、カラー偏光
板、光源、カラーフィルター、半透過反射板、反射板、
導光板、紫外線カットフィルター等を積層する、文字、
図形等を印刷する、ノングレア加工する等して液晶電気
光学素子とする。A composition containing the compound of the present invention is injected into this empty cell, and the injection port is sealed with a sealant to form a liquid crystal cell. If necessary, a polarizing plate, a color polarizing plate, a light source, a color filter, a semi-transmissive reflector, a reflector,
Laminated light guide plate, UV cut filter, etc., letters,
A liquid crystal electro-optical element is obtained by printing a figure or the like or performing non-glare processing.
【0052】なお、上述の説明は、液晶電気光学素子の
基本的な構成および製法を示したにすぎなく、例えば2
層電極を用いた基板、2層の液晶層を形成した2層液晶
セル、TFT、MIM等の能動素子を形成したアクティ
ブマトリクス基板を用いたアクティブマトリクス素子
等、種々の構成のものが使用できる。The above description merely shows the basic constitution and manufacturing method of the liquid crystal electro-optical element.
Various structures such as a substrate using a layer electrode, a two-layer liquid crystal cell in which two liquid crystal layers are formed, an active matrix element using an active matrix substrate in which active elements such as TFT and MIM are formed can be used.
【0053】本発明の化合物を液晶組成物に用いること
により、高デューティ駆動を行っても、高速応答が期待
できる。このため、近年注目されている高ツイスト角の
スーパーツイスト(STN)型液晶電気光学素子に好適
である。By using the compound of the present invention in a liquid crystal composition, a high speed response can be expected even when high duty driving is performed. Therefore, it is suitable for a super twist (STN) type liquid crystal electro-optical element having a high twist angle, which has been receiving attention in recent years.
【0054】その他、多色性色素を用いたGH型液晶表
示素子、強誘電性液晶電気光学素子等にも使用できる。
また、高比抵抗を有していることにより、電圧保持率が
高く、TFT型液晶電気光学素子にも好適である。In addition, it can also be used for a GH type liquid crystal display device using a polychromatic dye, a ferroelectric liquid crystal electro-optical device, and the like.
Further, since it has a high specific resistance, it has a high voltage holding ratio and is suitable for a TFT type liquid crystal electro-optical element.
【0055】本発明の一般式(1) の化合物は、例えば次
の方法にしたがって製造される。The compound of the general formula (1) of the present invention is produced, for example, according to the following method.
【0056】[0056]
【化8】 [Chemical 8]
【0057】なお、上記のA1、A2は相互に独立してトラ
ンス-1,4- シクロヘキシレン基、1-シクロヘキセン-1,4
- イレン基および1,4-フェニレン基から選ばれる環基で
あり、これらの環基は夫々非置換であるかあるいは置換
基として1個以上のハロゲン原子、シアノ基を有し、こ
れらの環基中環を構成する1個以上の=CH-基は窒素原子
に置換されていてもよく、また、環を構成する1個以上
の-CH2- 基は酸素原子もしくは硫黄原子に置換されてい
てもよい。The above A 1 and A 2 are independently of each other a trans-1,4-cyclohexylene group, 1-cyclohexene-1,4
-A ring group selected from an irene group and a 1,4-phenylene group, each of these ring groups being unsubstituted or having one or more halogen atoms or a cyano group as a substituent. One or more = CH- groups forming the middle ring may be substituted with a nitrogen atom, and one or more -CH 2 -groups forming the ring may be substituted with an oxygen atom or a sulfur atom. Good.
【0058】Y1、Y2は相互に独立して-COO- 、-OCO- 、
-C≡C-、-CH2CH2-、-CH=CH- 、-OCH2-、-CH2O-、-CF2CF
2-、-CF=CF- または単結合を示す。Y 1 and Y 2 are independently of each other -COO-, -OCO-,
-C≡C-, -CH 2 CH 2- , -CH = CH-, -OCH 2- , -CH 2 O-, -CF 2 CF
2- , -CF = CF- or indicates a single bond.
【0059】R は炭素数 1〜10のアルキル基、ハロゲン
原子あるいはシアノ基を示し、アルキル基の場合には、
このアルキル基中の炭素−炭素結合間あるいはこのアル
キル基と環基との間の炭素−炭素結合間に酸素原子、カ
ルボニルオキシ基、あるいはオキシカルボニル基が挿入
されてもよく、また、そのアルキル基中の炭素−炭素結
合の一部が三重結合あるいは二重結合に置換されていて
もよく、また、そのアルキル基内の1個の-CH2- 基がカ
ルボニル基に置換されていてもよく、また、そのアルキ
ル基中の水素原子の一部もしくはすべてがフッ素原子に
置換されていてもよい。R represents an alkyl group having 1 to 10 carbon atoms, a halogen atom or a cyano group, and in the case of an alkyl group,
An oxygen atom, a carbonyloxy group, or an oxycarbonyl group may be inserted between the carbon-carbon bond in the alkyl group or between the carbon-carbon bond between the alkyl group and the ring group. Part of the carbon-carbon bond in the may be replaced with a triple bond or a double bond, and one -CH 2- group in the alkyl group may be replaced with a carbonyl group, Further, some or all of the hydrogen atoms in the alkyl group may be replaced with fluorine atoms.
【0060】M はリチウムまたはマグネシウム等の金属
を示し、X は塩素原子、臭素原子またはヨウ素原子を示
す。m 、n は相互に独立して 0または 1を示す。M represents a metal such as lithium or magnesium, and X represents a chlorine atom, a bromine atom or an iodine atom. m and n independently represent 0 or 1.
【0061】また、「-In(F)」は5,6-ジフルオロインダ
ン-2- イル基を表し、「(F)Ph-」は3,4-ジフルオロフェ
ニレン基を表し、「1-InO(F)」は5,6-ジフルオロ-1- イ
ンダノン、「2-InO(F)」は5,6-ジフルオロ-2- インダノ
ン、「-Ind(F)」 は5,6-ジフルオロ-1H-インデン-2- イル
基を表す。"-In (F)" represents a 5,6-difluoroindan-2-yl group, "(F) Ph-" represents a 3,4-difluorophenylene group, and "1-InO ( F) "is 5,6-difluoro-1-indanone," 2-InO (F) "is 5,6-difluoro-2-indanone, and" -Ind (F) "is 5,6-difluoro-1H-indene. -2- represents an yl group.
【0062】式(15)の3,4-ジフルオロベンズアルデヒド
を塩基の存在下、マロン酸ジエチルと反応させることに
よって、式(16)のビニル化合物とする。The vinyl compound of formula (16) is obtained by reacting 3,4-difluorobenzaldehyde of formula (15) with diethyl malonate in the presence of a base.
【0063】次に、この化合物をパラジウム炭素の存在
下水素添加し、さらに酸によって脱炭酸反応させること
によって、式(18)のフェニルプロピオン酸化合物を得
る。Next, this compound is hydrogenated in the presence of palladium carbon, and further decarboxylated with an acid to obtain a phenylpropionic acid compound of the formula (18).
【0064】次いで、式(19)の酸クロリドに変換後、フ
リーデル・クラフツ反応によって環化反応させて、式(2
0)の1-インダノン化合物とし、さらに還元、脱水によっ
て式(21)のインデン化合物を得る。Then, after conversion to the acid chloride of the formula (19), cyclization reaction is carried out by the Friedel-Crafts reaction to give the compound of the formula (2
The 1-indanone compound of (0) is further reduced and dehydrated to obtain the indene compound of the formula (21).
【0065】そして、さらに酸化してジオールのモノぎ
酸エステルとした後、脱水して式(22)の2-インダノン化
合物とする。Then, it is further oxidized to form a monoformate ester of diol and then dehydrated to give a 2-indanone compound of the formula (22).
【0066】最後に、式(23)の金属化合物と反応させて
アルコールとした後、脱水し、さらに得られたインデン
誘導体を水素添加して式(1) のインダン誘導体化合物を
得る。Finally, after reacting with the metal compound of formula (23) to form an alcohol, it is dehydrated, and the obtained indene derivative is hydrogenated to obtain an indane derivative compound of formula (1).
【0067】また、一般式(1) の化合物のR にアシル基
を導入する方法は、R が水素原子である一般式(1) の化
合物とアシルハライドとのフリーデル・クラフツ反応を
用いればよい。また、一般式(1) の化合物のR にシアノ
基を導入する方法は、R が臭素原子またはヨウ素原子で
ある一般式(1) の化合物をCuCNと反応させればよい。As a method for introducing an acyl group into R 1 of the compound of the general formula (1), the Friedel-Crafts reaction between the compound of the general formula (1) in which R 2 is a hydrogen atom and the acyl halide may be used. . Further, the method of introducing a cyano group into R 1 of the compound of general formula (1) may be to react the compound of general formula (1) in which R 2 is a bromine atom or an iodine atom with CuCN.
【0068】また、R,A1,Y1,A2のいずれかに不飽和結合
を有する化合物は、以下のようにして得ることができ
る。A compound having an unsaturated bond in any of R, A 1 , Y 1 and A 2 can be obtained as follows.
【0069】[0069]
【化9】 [Chemical 9]
【0070】すなわち、末端基にハロゲンを有する化合
物(24)とR,A1,Y1,A2のいずれかに不飽和結合を有する金
属化合物(25)とを触媒を用いてカップリングさせること
により、得ることができる。That is, the compound (24) having a halogen at the terminal group and the metal compound (25) having an unsaturated bond in any of R, A 1 , Y 1 and A 2 are coupled by using a catalyst. Can be obtained.
【0071】また、Y2が-CH=CH- や-C≡C-である化合物
は、以下のようにして得ることができる。A compound in which Y 2 is —CH═CH— or —C≡C— can be obtained as follows.
【0072】[0072]
【化10】 [Chemical 10]
【0073】すなわち、インダン化合物(26)を還元剤に
よって式(27)のアルコール化合物とし、次いでこれを脱
水剤によって脱水することにより、Y2が-CH=CH- である
化合物(1A)を得ることができる。なお、p-TsOHはパラト
ルエンスルホン酸を表す。That is, the indane compound (26) is converted to an alcohol compound of the formula (27) with a reducing agent and then dehydrated with a dehydrating agent to obtain a compound (1A) in which Y 2 is —CH═CH—. be able to. In addition, p-TsOH represents paratoluenesulfonic acid.
【0074】また、式(1A)のエチレン化合物に臭素を付
加して、式(28)のジブロモ化合物とし、次いでこれを塩
基を用いて脱HBr することによりY2が-C≡C-である化合
物(1B)を得ることができる。Further, bromine is added to the ethylene compound of the formula (1A) to give a dibromo compound of the formula (28), which is then de-HBred with a base to give Y 2 -C≡C-. The compound (1B) can be obtained.
【0075】[0075]
実施例1 [第1ステップ]冷却管付きの2000mlの三ツ口フラスコ
に3,4-ジフルオロベンズアルデヒド60g(0.42mol)、マロ
ン酸ジエチル64g(0.4mol) 、ピペリジン4g(0.047mol)お
よびトルエン800ml を仕込み、140 ℃にて12時間反応さ
せた。冷却後、1N塩酸を200ml 加え、有機層を分離し
た。水層をトルエンで抽出後、有機層に加え、水洗、乾
燥後、溶媒を留去した。次いで、カラムクロマトグラフ
ィーにて精製して、3,4-ジフルオロベンザルマロン酸ジ
エチルを92.8g(収率82%)得た。 (F)Ph-CH=C(COOEt)2 Example 1 [First Step] A 2000 ml three-necked flask equipped with a cooling tube was charged with 60 g (0.42 mol) of 3,4-difluorobenzaldehyde, 64 g (0.4 mol) of diethyl malonate, 4 g (0.047 mol) of piperidine and 800 ml of toluene, The reaction was carried out at 140 ° C for 12 hours. After cooling, 200 ml of 1N hydrochloric acid was added, and the organic layer was separated. The aqueous layer was extracted with toluene, added to the organic layer, washed with water, dried and the solvent was distilled off. Then, it was purified by column chromatography to obtain 92.8 g (yield: 82%) of diethyl 3,4-difluorobenzalmalonate. (F) Ph-CH = C (COOEt) 2
【0076】[0076]
【化11】 [Chemical 11]
【0077】本化合物の分析結果を以下に示す。ただ
し、m はマルチプレットを表す。19 F-NMR(CDCl3) δppm from CFCl3;-133.7ppm(m),-13
6.6ppm(m) MS m/e 284(M+)The analysis results of this compound are shown below. However, m represents a multiplet. 19 F-NMR (CDCl 3 ) δppm from CFCl 3 ; -133.7ppm (m),-13
6.6ppm (m) MS m / e 284 (M + )
【0078】[第2ステップ]次に、得られた3,4-ジフ
ルオロベンザルマロン酸ジエチル92.8g(0.33mol)を400m
l のエチルアルコールに溶解し、10%パラジウム炭素10
g を加え、常圧下で水素を添加して、室温で12時間反応
させた。ろ過後、溶媒を留去し、カラムクロマトグラフ
ィーにて精製して、3,4-ジフルオロベンジルマロン酸ジ
エチル90.1g(収率97%)を得た。 (F)Ph-CH2CH(COOEt)2 [Second Step] Next, 92.8 g (0.33 mol) of the obtained diethyl 3,4-difluorobenzalmalonate was added to 400 m.
10% Palladium on carbon 10 dissolved in l ethyl alcohol
g was added, hydrogen was added under normal pressure, and the mixture was reacted at room temperature for 12 hours. After filtration, the solvent was distilled off, and the residue was purified by column chromatography to obtain 90.1 g (yield 97%) of diethyl 3,4-difluorobenzylmalonate. (F) Ph-CH 2 CH (COOEt) 2
【0079】[0079]
【化12】 [Chemical 12]
【0080】本化合物の分析結果を以下に示す。19 F-NMR(CDCl3) δppm from CFCl3;-138.3ppm(m),-14
1.0ppm(m) MS m/e 286(M+)The analysis results of this compound are shown below. 19 F-NMR (CDCl 3 ) δppm from CFCl 3 ; -138.3ppm (m),-14
1.0ppm (m) MS m / e 286 (M + )
【0081】[第3ステップ]次に、得られた3,4-ジフ
ルオロベンジルマロン酸ジエチル90.1g(0.32mol)に、47
%HBr 水溶液500ml を加え、120 ℃にて3 時間反応させ
た。冷却後、酢酸エチルを加え、有機層を分離した。水
層を酢酸エチルで抽出後、有機層に加え、水洗、乾燥
後、溶媒を留去し粗結晶58g を得た。次いで、ヘキサン
溶媒で再結晶し3-(3,4- ジフルオロフェニル) プロピオ
ン酸53.3g(収率91%)を得た。 (F)Ph-CH2CH2COOH[Third step] Next, to 90.1 g (0.32 mol) of the obtained diethyl 3,4-difluorobenzylmalonate, 47
% HBr aqueous solution (500 ml) was added and reacted at 120 ° C. for 3 hours. After cooling, ethyl acetate was added and the organic layer was separated. The aqueous layer was extracted with ethyl acetate, added to the organic layer, washed with water and dried, and then the solvent was distilled off to obtain 58 g of crude crystals. Then, it was recrystallized with a hexane solvent to obtain 53.3 g (yield 91%) of 3- (3,4-difluorophenyl) propionic acid. (F) Ph-CH 2 CH 2 COOH
【0082】[0082]
【化13】 [Chemical 13]
【0083】本化合物の分析結果を以下に示す。19 F-NMR(CDCl3) δppm from CFCl3;-138.3ppm(m),-14
1.7ppm(m) MS m/e 186(M+)The analysis results of this compound are shown below. 19 F-NMR (CDCl 3 ) δppm from CFCl 3 ; -138.3ppm (m),-14
1.7ppm (m) MS m / e 186 (M + )
【0084】[第4ステップ]次に、得られた3-(3,4-
ジフルオロフェニル) プロピオン酸53.3g(0.29mol)に、
SOCl2 51g(0.42mol)を加え、80℃にて2 時間反応させ
た。未反応のSOCl2 を留去後、3-(3,4- ジフルオロフェ
ニル) プロピオン酸クロリドを蒸留により42.8g(収率73
%)得た。(b.p.86.5〜86.9℃/4mmHg) (F)Ph-CH2CH2COCl[Fourth Step] Next, the obtained 3- (3,4-
Difluorophenyl) propionic acid 53.3 g (0.29 mol),
SOCl 2 51g (0.42mol) was added and reacted at 80 ° C for 2 hours. After distilling off unreacted SOCl 2 , 4-2.8 g (yield 73%) of 3- (3,4-difluorophenyl) propionic acid chloride was distilled.
%)Obtained. (Bp86.5 to 86.9 ℃ / 4mmHg) (F) Ph-CH 2 CH 2 COCl
【0085】[0085]
【化14】 [Chemical 14]
【0086】本化合物の分析結果を以下に示す。19 F-NMR(CDCl3) δppm from CFCl3;-136.7ppm(m),-13
9.2ppm(m) MS m/e 204(M+)The analysis results of this compound are shown below. 19 F-NMR (CDCl 3 ) δppm from CFCl 3 ; -136.7ppm (m),-13
9.2ppm (m) MS m / e 204 (M + )
【0087】[第5ステップ]次に、得られた3-(3,4-
ジフルオロフェニル) プロピオン酸クロリド42.8g(0.21
mol)に、CH2Cl2 1000ml を加え0 ℃に冷却し AlCl3 42g
(0.31mol) を徐々に加えた。室温で3 時間反応後、氷水
を加えエーテルで抽出し、抽出液を水、水酸化ナトリウ
ム水溶液、食塩水で洗浄、乾燥した。そして、溶媒を留
去することにより粗結晶33g を得た。次いで、ヘキサン
溶媒で再結晶し5,6-ジフルオロ-1- インダノン29.5g(収
率84%)を得た。 1-InO(F)[Fifth Step] Next, the obtained 3- (3,4-
Difluorophenyl) propionyl chloride 42.8 g (0.21
CH 2 Cl 2 ( 1000 ml) and cooled to 0 ° C. AlCl 3 42 g
(0.31 mol) was added slowly. After reacting at room temperature for 3 hours, ice water was added and the mixture was extracted with ether. The extract was washed with water, aqueous sodium hydroxide solution and brine and dried. Then, the solvent was distilled off to obtain 33 g of crude crystals. Then, it was recrystallized with a hexane solvent to obtain 29.5 g (yield 84%) of 5,6-difluoro-1-indanone. 1-InO (F)
【0088】[0088]
【化15】 [Chemical 15]
【0089】本化合物の分析結果を以下に示す。19 F-NMR(CDCl3) δppm from CFCl3;-126.4ppm(m),-13
7.6ppm(m) MS m/e 168(M+)The analysis results of this compound are shown below. 19 F-NMR (CDCl 3 ) δppm from CFCl 3 ; -126.4ppm (m),-13
7.6ppm (m) MS m / e 168 (M + )
【0090】[第6ステップ]次に、得られた5,6-ジフ
ルオロ-1- インダノン29.5g(0.18mol)をエタノール500m
l に溶解し、NaBH4 3.4g(0.09mol) を徐々に加えた。室
温で5 時間反応させ、水を加えエタノールを減圧留去後
トルエンで抽出した。抽出液を乾燥後、300mlまで濃縮
し、p-トルエンスルホン酸0.2gを加え、3 時間加熱還流
した。冷却後、5 %炭酸水素ナトリウム水溶液を加え洗
浄後、有機層を分離し、乾燥、溶媒留去した。次いで、
カラムクロマトグラフィーにて精製して、5,6-ジフルオ
ロ-1H-インデン26.5g(収率97%)を得た。 H-Ind(F)[Sixth Step] Next, 29.5 g (0.18 mol) of the obtained 5,6-difluoro-1-indanone was added to 500 m of ethanol.
It was dissolved in l and 3.4 g (0.09 mol) of NaBH 4 was gradually added. The mixture was reacted at room temperature for 5 hours, water was added, ethanol was distilled off under reduced pressure, and the mixture was extracted with toluene. The extract was dried and concentrated to 300 ml, 0.2 g of p-toluenesulfonic acid was added, and the mixture was heated under reflux for 3 hours. After cooling, 5% aqueous sodium hydrogencarbonate solution was added and washed, then the organic layer was separated, dried and the solvent was distilled off. Then
Purification by column chromatography gave 26.5 g (yield 97%) of 5,6-difluoro-1H-indene. H-Ind (F)
【0091】[0091]
【化16】 [Chemical 16]
【0092】本化合物の分析結果を以下に示す。 MS m/e 152(M+)The analysis results of this compound are shown below. MS m / e 152 (M + )
【0093】[第7ステップ]次に、ぎ酸120ml と過酸
化水素水24ml(0.23mol) の混合液に、先に得られた5,6-
ジフルオロ-1H-インデン26.5g(0.17mol)を徐々に加え、
室温で7 時間反応させた。ぎ酸を減圧留去した後、沸騰
している7 %硫酸水溶液にこれを加え、水蒸気蒸留によ
り得られた結晶を乾燥し5,6-ジフルオロ-2- インダノン
21.1g(収率74%)を得た。 2-InO(F)[Seventh Step] Next, a mixture of 120 ml of formic acid and 24 ml (0.23 mol) of hydrogen peroxide was added to the previously obtained 5,6-
Difluoro-1H-indene 26.5 g (0.17 mol) was gradually added,
The reaction was carried out at room temperature for 7 hours. After distilling off formic acid under reduced pressure, this was added to boiling 7% aqueous sulfuric acid solution, and the crystals obtained by steam distillation were dried to give 5,6-difluoro-2-indanone.
21.1 g (74% yield) was obtained. 2-InO (F)
【0094】[0094]
【化17】 [Chemical 17]
【0095】本化合物の分析結果を以下に示す。 MS m/e 168(M+)The analysis results of this compound are shown below. MS m / e 168 (M + )
【0096】[第8ステップ]冷却管付きの100ml の三
ツ口フラスコに無水エーテル(EtOEt) を30ml入れ、-78
℃に冷却した。ここに1-ヨード−4-n-プロピルベンゼン
を1.6g(6.6mmol) 加え、次いで、n-ブチルリチウムのn-
ヘキサン溶液(1.65M) 4.0ml(6.6mmol)を徐々に滴下し、
さらに30分撹拌した。次に、これを第7ステップで合成
した5,6-ジフルオロ-2- インダノン1.0g(6.0mmol) のエ
ーテル溶液に-78 ℃にて滴下した。[Eighth step] 30 ml of anhydrous ether (EtOEt) was put into a 100 ml three-necked flask equipped with a cooling tube, and -78
Cooled to ° C. To this, 1.6 g (6.6 mmol) of 1-iodo-4-n-propylbenzene was added, and then n-butyllithium n-
Hexane solution (1.65M) 4.0ml (6.6mmol) was slowly added dropwise,
It was stirred for another 30 minutes. Next, this was added dropwise to an ether solution of 1.0 g (6.0 mmol) of 5,6-difluoro-2-indanone synthesized in the seventh step at -78 ° C.
【0097】さらに、室温まで昇温し、4時間撹拌後、
1N塩酸水溶液を加え、有機層を分離した。水層をエーテ
ルで抽出し、有機層を合わせて水洗、乾燥後、溶媒を留
去し、2-(4-n- プロピルフェニル)-5,6-ジフルオロイン
ダン-2- オールを1.5g( 収率87%)得た。Further, the temperature was raised to room temperature, and after stirring for 4 hours,
A 1N aqueous hydrochloric acid solution was added, and the organic layer was separated. The aqueous layer was extracted with ether, the organic layers were combined, washed with water, dried, and the solvent was evaporated to give 1.5 g of 2- (4-n-propylphenyl) -5,6-difluoroindan-2-ol. Rate 87%).
【0098】[第9ステップ]次に、得られた2-(4-n-
プロピルフェニル)-5,6-ジフルオロインダン-2- オール
1.5g(5.2mmol) を30mlのトルエンに溶解し、硫酸水素カ
リウムを0.1g加え、3時間加熱還流させた。冷却後、水
を加え、有機層を分離した。水層をエーテルで抽出し、
有機層を合わせて水洗、乾燥後、溶媒を留去し、得られ
た粗結晶をシリカゲルカラムクロマトグラフィーにて精
製して、2-(4-n- プロピルフェニル)-5,6-ジフルオロ-1
H-インデンを1.3g( 収率93%)得た。 n-C3H7-Ph-Ind(F)[Ninth Step] Next, the obtained 2- (4-n-
Propylphenyl) -5,6-difluoroindan-2-ol
1.5 g (5.2 mmol) was dissolved in 30 ml of toluene, 0.1 g of potassium hydrogen sulfate was added, and the mixture was heated under reflux for 3 hours. After cooling, water was added and the organic layer was separated. Extract the aqueous layer with ether,
The organic layers were combined, washed with water and dried, then the solvent was distilled off, and the obtained crude crystals were purified by silica gel column chromatography to give 2- (4-n-propylphenyl) -5,6-difluoro-1.
1.3 g (yield 93%) of H-indene was obtained. nC 3 H 7 -Ph-Ind (F)
【0099】[0099]
【化18】 [Chemical 18]
【0100】本化合物の分析結果を以下に示す。 MS m/e 270(M+)The analysis results of this compound are shown below. MS m / e 270 (M + )
【0101】[第10ステップ]次に、得られた2-(4-n
- プロピルフェニル)-5,6-ジフルオロ-1H-インデン1.3g
を50mlのトルエンに溶解し、酸化白金触媒0.5gを加え、
60℃に加温し、常圧で接触還元を行って、4時間で計算
量の水素を付加させた。触媒を濾別後、溶媒を減圧留去
し、得られた粗結晶をシリカゲルカラムクロマトグラフ
ィーにて精製して、2-(4-n- プロピルフェニル)-5,6-ジ
フルオロインダンを1.2g (収率90%) 得た。 n-C3H7-Ph-In(F)[Tenth Step] Next, the obtained 2- (4-n
-Propylphenyl) -5,6-difluoro-1H-indene 1.3 g
Was dissolved in 50 ml of toluene, 0.5 g of platinum oxide catalyst was added,
The mixture was heated to 60 ° C., catalytic reduction was carried out under normal pressure, and a calculated amount of hydrogen was added in 4 hours. After the catalyst was filtered off, the solvent was distilled off under reduced pressure, and the resulting crude crystals were purified by silica gel column chromatography to give 1.2 g of 2- (4-n-propylphenyl) -5,6-difluoroindane. Yield 90%). nC 3 H 7 -Ph-In (F)
【0102】[0102]
【化19】 [Chemical 19]
【0103】本化合物の分析結果を以下に示す。 MS m/e 272(M+)The analysis results of this compound are shown below. MS m / e 272 (M + )
【0104】実施例1と同様にして、以下の化合物を得
ることができる。 CH3-Ph-In(F) n-C5H11-Ph-In(F) CF3-Ph-In(F) (F)Ph-In(F) CH3O-Ph-In(F) n-C3H7O-Ph-In(F)The following compounds can be obtained in the same manner as in Example 1. CH 3 -Ph-In (F) nC 5 H 11 -Ph-In (F) CF 3 -Ph-In (F) (F) Ph-In (F) CH 3 O-Ph-In (F) nC 3 H 7 O-Ph-In (F)
【0105】実施例2 アルゴン雰囲気下、還流管付きの 100ml三ツ口フラスコ
にマグネシウム0.17g(7.0mmol)および乾燥テトラヒドロ
フラン(THF)10mlを入れた。次いで、1-ブロモプロ
パンを数滴加え、さらにトランス-1- クロロ-4-n- プロ
ピルシクロヘキサン1.1g(6.9mmol) を発熱が続く速度で
滴下した。滴下終了後、さらに 1時間還流を続けた後、
室温まで放冷した。Example 2 Under an argon atmosphere, 0.17 g (7.0 mmol) of magnesium and 10 ml of dry tetrahydrofuran (THF) were placed in a 100 ml three-necked flask equipped with a reflux tube. Then, a few drops of 1-bromopropane were added, and 1.1 g (6.9 mmol) of trans-1-chloro-4-n-propylcyclohexane was added dropwise at a rate at which heat generation continued. After the dropping was completed, the reflux was continued for another hour,
It was left to cool to room temperature.
【0106】次に、別途調製した5,6-ジメチル-2- イン
ダノン1.0g(6.0mmol) のエーテル溶液の中に上記溶液を
10℃以下にて滴下した。さらに、室温まで昇温し、4時
間撹拌後、1N塩酸水溶液を加え、有機層を分離した。水
層をエーテルで抽出し、有機層を合わせて水洗、乾燥
後、溶媒を留去し、2-( トランス-4-n- プロピルシクロ
ヘキシル)-5,6-ジフルオロインダン-2- オールを1.4g(
収率80%)得た。Next, the above solution was added to a separately prepared ether solution of 1.0 g (6.0 mmol) of 5,6-dimethyl-2-indanone.
It was added dropwise at 10 ° C or lower. Furthermore, the temperature was raised to room temperature, and after stirring for 4 hours, a 1N hydrochloric acid aqueous solution was added, and the organic layer was separated. The aqueous layer was extracted with ether, the organic layers were combined, washed with water, dried and the solvent was distilled off to give 1.4 g of 2- (trans-4-n-propylcyclohexyl) -5,6-difluoroindan-2-ol. (
Yield 80%).
【0107】以下、実施例1と同様に反応を行い、2-(
トランス-4-n- プロピルシクロヘキシル)-5,6-ジフルオ
ロインダンを1.1g( 収率90%)得た。 n-C3H7-Cy-In(F)Thereafter, the reaction is carried out in the same manner as in Example 1 to give 2- (
1.1 g (yield 90%) of trans-4-n-propylcyclohexyl) -5,6-difluoroindane was obtained. nC 3 H 7 -Cy-In (F)
【0108】[0108]
【化20】 [Chemical 20]
【0109】本化合物の分析結果を以下に示す。 MS m/e 278(M+)The analysis results of this compound are shown below. MS m / e 278 (M + )
【0110】実施例2と同様にして、以下の化合物を得
ることができる。 CH3-Cy-In(F) n-C5H11-Cy-In(F) CF3-Cy-In(F) F-Cy-In(F) CH3O-Cy-In(F) n-C3H7O-Cy-In(F)The following compounds can be obtained in the same manner as in Example 2. CH 3 -Cy-In (F) nC 5 H 11 -Cy-In (F) CF 3 -Cy-In (F) F-Cy-In (F) CH 3 O-Cy-In (F) nC 3 H 7 O-Cy-In (F)
【0111】実施例3 実施例1において、1-ヨード-4-n- プロピルベンゼンの
かわりに4-( トランス-4-n- プロピルシクロヘキシル)
ブロモベンゼンを1.9g(6.8mmol) 用いる以外は実施例1
と同様に反応を行い、2-[4-(トランス-4-n- プロピルシ
クロヘキシル)フェニル]-5,6-ジフルオロインダンを1.
5g( 収率71%)得た。 n-C3H7-Cy-Ph-In(F)Example 3 In Example 1, 4- (trans-4-n-propylcyclohexyl) was used instead of 1-iodo-4-n-propylbenzene.
Example 1 except that 1.9 g (6.8 mmol) of bromobenzene was used
The reaction is performed in the same manner as in, and 2- [4- (trans-4-n-propylcyclohexyl) phenyl] -5,6-difluoroindane is added to 1.
5 g (yield 71%) was obtained. nC 3 H 7 -Cy-Ph-In (F)
【0112】[0112]
【化21】 [Chemical 21]
【0113】本化合物の分析結果を以下に示す。 MS m/e 354(M+)The analysis results of this compound are shown below. MS m / e 354 (M + )
【0114】実施例3と同様にして、以下の化合物を得
ることができる。 CF3-Cy-Ph-In(F) F-Cy-Ph-In(F) CH3CH2O-Cy-Ph-In(F) CF3-Ph-Ph-In(F) F-Ph-Ph-In(F) CH3CH2O-Ph-Ph-In(F) CF3-Ch-Ph-In(F) F-Ch-Ph-In(F) CH3CH2O-Ch-Ph-In(F)The following compounds can be obtained in the same manner as in Example 3. CF 3 -Cy-Ph-In (F) F-Cy-Ph-In (F) CH 3 CH 2 O-Cy-Ph-In (F) CF 3 -Ph-Ph-In (F) F-Ph- Ph-In (F) CH 3 CH 2 O-Ph-Ph-In (F) CF 3 -Ch-Ph-In (F) F-Ch-Ph-In (F) CH 3 CH 2 O-Ch-Ph -In (F)
【0115】n-C3H7-Ph-OCO-Ph-In(F) n-C3H7-Ph-COO-Ph-In(F) n-C3H7-Ph-CH2CH2-Ph-In(F) n-C3H7-Ph-CH2O-Ph-In(F) n-C3H7-Ph-OCH2-Ph-In(F) n-C3H7-Ph-CF2CF2-Ph-In(F)NC 3 H 7 -Ph-OCO-Ph-In (F) nC 3 H 7 -Ph-COO-Ph-In (F) nC 3 H 7 -Ph-CH 2 CH 2 -Ph-In (F ) nC 3 H 7 -Ph-CH 2 O-Ph-In (F) nC 3 H 7 -Ph-OCH 2 -Ph-In (F) nC 3 H 7 -Ph-CF 2 CF 2 -Ph-In ( F)
【0116】実施例4 実施例2において、トランス-1- クロロ-4-n- プロピル
シクロヘキサンのかわりにトランス-1- クロロ-4-(トラ
ンス-4-n- プロピルシクロヘキシル)シクロヘキサン1.
6g(6.6mmol) を用いる以外は実施例2と同様に反応を行
い、2-[ トランス-4-(トランス-4-n- プロピルシクロヘ
キシル)シクロヘキシル]-5,6-ジフルオロインデンを1.
6g( 収率74%)得た。 n-C3H7-Cy-Cy-In(F)Example 4 In Example 2, trans-1-chloro-4- (trans-4-n-propylcyclohexyl) cyclohexane was used in place of trans-1-chloro-4-n-propylcyclohexane.
The reaction was performed in the same manner as in Example 2 except that 6 g (6.6 mmol) was used, and 2- [trans-4- (trans-4-n-propylcyclohexyl) cyclohexyl] -5,6-difluoroindene was added to 1.
6 g (yield 74%) was obtained. nC 3 H 7 -Cy-Cy-In (F)
【0117】[0117]
【化22】 [Chemical formula 22]
【0118】本化合物の分析結果を以下に示す。 MS m/e 360(M+)The analysis results of this compound are shown below. MS m / e 360 (M + )
【0119】実施例4と同様にして、以下の化合物を得
ることができる。 CF3-Cy-Cy-In(F) F-Cy-Cy-In(F) CH3CH2O-Cy-Cy-In(F) CF3-Ph-Cy-In(F) F-Ph-Cy-In(F) CH3CH2O-Ph-Cy-In(F) CF3-Ch-Cy-In(F) F-Ch-Cy-In(F) CH3CH2O-Ch-Cy-In(F)The following compounds can be obtained in the same manner as in Example 4. CF 3 -Cy-Cy-In (F) F-Cy-Cy-In (F) CH 3 CH 2 O-Cy-Cy-In (F) CF 3 -Ph-Cy-In (F) F-Ph- Cy-In (F) CH 3 CH 2 O-Ph-Cy-In (F) CF 3 -Ch-Cy-In (F) F-Ch-Cy-In (F) CH 3 CH 2 O-Ch-Cy -In (F)
【0120】n-C3H7-Ph-OCO-Cy-In(F) n-C3H7-Ph-COO-Cy-In(F) n-C3H7-Ph-CH2CH2-Cy-In(F) n-C3H7-Ph-CH2O-Cy-In(F) n-C3H7-Ph-OCH2-Cy-In(F) n-C3H7-Ph-CF2CF2-Cy-In(F)NC 3 H 7 -Ph-OCO-Cy-In (F) nC 3 H 7 -Ph-COO-Cy-In (F) nC 3 H 7 -Ph-CH 2 CH 2 -Cy-In (F ) nC 3 H 7 -Ph-CH 2 O-Cy-In (F) nC 3 H 7 -Ph-OCH 2 -Cy-In (F) nC 3 H 7 -Ph-CF 2 CF 2 -Cy-In ( F)
【0121】実施例5 実施例1において、1-ヨード-4-n- プロピルベンゼンの
かわりに2-ブロモ-5-n- プロピルピリミジンを1.3g(6.5
mmol) 用いる以外は実施例1と同様に反応を行い、2-(5
-n- プロピルピリミジン-2- イル)-5,6-ジフルオロイン
ダンを1.2g( 収率74%)得た。なお、-Py-はピリミジン
−2,5-ジイル基を表す。 n-C3H7-Py-In(F)Example 5 In Example 1, 1.3 g (6.5 g) of 2-bromo-5-n-propylpyrimidine was used instead of 1-iodo-4-n-propylbenzene.
mmol) was used, and the reaction was performed in the same manner as in Example 1, and
1.2 g (yield 74%) of -n-propylpyrimidin-2-yl) -5,6-difluoroindane was obtained. In addition, -Py- represents a pyrimidine-2,5-diyl group. nC 3 H 7 -Py-In (F)
【0122】[0122]
【化23】 [Chemical formula 23]
【0123】本化合物の分析結果を以下に示す。 MS m/e 274(M+)The analysis results of this compound are shown below. MS m / e 274 (M + )
【0124】実施例5と同様にして、以下の化合物を得
ることができる。 CH3-Py-In(F) n-C5H11-Py-In(F) CF3-Py-In(F) F-Py-In(F) CH3O-Py-In(F) n-C3H7O-Py-In(F)The following compounds can be obtained in the same manner as in Example 5. CH 3 -Py-In (F) nC 5 H 11 -Py-In (F) CF 3 -Py-In (F) F-Py-In (F) CH 3 O-Py-In (F) nC 3 H 7 O-Py-In (F)
【0125】実施例6 実施例1において、1-ヨード-4-n- プロピルベンゼンの
かわりに2-n-プロピル-5- ブロモ-1,3- ジオキサンを1.
4g(6.7mmol) 用いる以外は実施例1と同様に反応を行
い、2-(4-n- プロピル-3,5- ジオキサン-2−イル)-5,6-
ジフルオロインダンを1.2g(収率69%)得た。なお、-D
o-は1,3-ジオキサン-2,5- ジイル基を表す。 n-C3H7-Do-In(F)Example 6 In Example 1, 2-n-propyl-5-bromo-1,3-dioxane was replaced by 1.n instead of 1-iodo-4-n-propylbenzene.
The reaction was performed in the same manner as in Example 1 except that 4 g (6.7 mmol) was used, and 2- (4-n-propyl-3,5-dioxan-2-yl) -5,6- was used.
1.2 g (yield 69%) of difluoroindane was obtained. Note that -D
o- represents a 1,3-dioxane-2,5-diyl group. nC 3 H 7 -Do-In (F)
【0126】[0126]
【化24】 [Chemical formula 24]
【0127】本化合物の分析結果を以下に示す。 MS m/e 282(M+)The analysis results of this compound are shown below. MS m / e 282 (M + )
【0128】実施例6と同様にして、以下の化合物を得
ることができる。 CH3-Do-In(F) n-C5H11-Do-In(F) CF3-Do-In(F) F-Do-In(F) CH3O-Do-In(F) n-C3H7O-Do-In(F)The following compounds can be obtained in the same manner as in Example 6. CH 3 -Do-In (F) nC 5 H 11 -Do-In (F) CF 3 -Do-In (F) F-Do-In (F) CH 3 O-Do-In (F) nC 3 H 7 O-Do-In (F)
【0129】実施例7 実施例2において、トランス-1- クロロ-4-n- プロピル
シクロヘキサンのかわりに1-ブロモプロパンを0.8g(6.5
mmol) 用いる以外は実施例2と同様に反応を行い、2-n-
プロピル-5,6- ジフルオロインダンを0.8g( 収率71%)
得た。 n-C3H7-In(F)Example 7 In Example 2, 0.8 g (6.5 g) of 1-bromopropane was used instead of trans-1-chloro-4-n-propylcyclohexane.
mmol), except that the reaction is performed in the same manner as in Example 2, and 2-n-
Propyl-5,6-difluoroindane 0.8g (71% yield)
Obtained. nC 3 H 7 -In (F)
【0130】[0130]
【化25】 [Chemical 25]
【0131】本化合物の分析結果を以下に示す。 MS m/e 196(M+)The analysis results of this compound are shown below. MS m / e 196 (M + )
【0132】実施例7と同様にして、以下の化合物を得
ることができる。 CH3-In(F) n-C5H11-In(F) CF3CH2CH2-In(F)The following compounds can be obtained in the same manner as in Example 7. CH 3 -In (F) nC 5 H 11 -In (F) CF 3 CH 2 CH 2 -In (F)
【0133】実施例8 実施例2において、トランス-1- クロロ-4-n- プロピル
シクロヘキサンのかわりに4-n-プロピルフェネチルブロ
ミドを1.5g(6.6mmol) 用いる以外は実施例2と同様に反
応を行い、2-(4-n- プロピルフェネチル)-5,6-ジフルオ
ロインダンを1.2g( 収率67%)得た。 n-C3H7-Ph-CH2CH2-In(F)Example 8 Reaction was performed in the same manner as in Example 2 except that 1.5 g (6.6 mmol) of 4-n-propylphenethyl bromide was used instead of trans-1-chloro-4-n-propylcyclohexane. Then, 1.2 g (yield 67%) of 2- (4-n-propylphenethyl) -5,6-difluoroindane was obtained. nC 3 H 7 -Ph-CH 2 CH 2 -In (F)
【0134】[0134]
【化26】 [Chemical formula 26]
【0135】本化合物の分析結果を以下に示す。 MS m/e 300(M+)The analysis results of this compound are shown below. MS m / e 300 (M + )
【0136】実施例8と同様にして、以下の化合物を得
ることができる。 n-C3H7-Cy-CH2CH2-In(F) n-C3H7-Ch-CH2CH2-In(F) n-C3H7O-Ph-CH2CH2-In(F)The following compounds can be obtained in the same manner as in Example 8. nC 3 H 7 -Cy-CH 2 CH 2 -In (F) nC 3 H 7 -Ch-CH 2 CH 2 -In (F) nC 3 H 7 O-Ph-CH 2 CH 2 -In (F)
【0137】実施例9 [第1ステップ]冷却管付きの 100mlの三ツ口フラスコ
に五塩化リン 7.5g(36mmol) および乾燥塩化メチレンを
50ml 入れ、0 ℃にて5,6-ジフルオロ-2- インダノン3.
0g(18mmol)を滴下した。滴下後さらに6時間還流した。
冷却後、氷水にあけ、有機層を分離した。水層を塩化メ
チレンで抽出し、有機層を合わせて水洗、乾燥後、溶媒
を留去し、2-クロロ-5,6- ジフルオロインデンを2.0g
(収率60%)得た。Example 9 [First Step] 7.5 g (36 mmol) of phosphorus pentachloride and dry methylene chloride were placed in a 100 ml three-necked flask equipped with a cooling tube.
Add 50 ml and stir 5,6-difluoro-2-indanone at 0 ° C 3.
0 g (18 mmol) was added dropwise. After the dropping, the mixture was refluxed for 6 hours.
After cooling, the mixture was poured into ice water and the organic layer was separated. The aqueous layer was extracted with methylene chloride, the organic layers were combined, washed with water, dried and evaporated to remove 2-chloro-5,6-difluoroindene (2.0 g).
(Yield 60%) was obtained.
【0138】[第2ステップ]次いで、冷却管およびガ
ス吹込管付きの100ml の三ツ口フラスコに乾燥エーテル
20ml、リチウムワイヤー0.15g(21.6mmol) およびヨウ素
を入れ、激しく撹拌しながら上記で得られた2-クロロ-
5,6- ジフルオロインデン2.0g(10.7mmol)を発熱が続く
速度で滴下した。滴下終了後、室温で6時間撹拌した。
次いで、0 ℃に冷却し、撹拌しながら二酸化炭素ガス4.
7g(107mmol) を30分かけて吹き込んだ。さらに室温で1
時間撹拌後、1N塩酸を加え、有機層を分離した。水層を
エーテルで抽出し、有機層を合わせて水洗、乾燥後、溶
媒を留去し、5,6-ジフルオロインデン-2- カルボン酸を
1.8g(収率86%)得た。[Second Step] Then, dry ether was placed in a 100 ml three-necked flask equipped with a cooling tube and a gas blowing tube.
20 ml, lithium wire 0.15 g (21.6 mmol) and iodine were added, and the 2-chloro-
2.0 g (10.7 mmol) of 5,6-difluoroindene was added dropwise at such a rate that the exotherm continued. After completion of dropping, the mixture was stirred at room temperature for 6 hours.
Then cool to 0 ° C and carbon dioxide gas with stirring 4.
7 g (107 mmol) were bubbled in over 30 minutes. 1 at room temperature
After stirring for 1 hour, 1N hydrochloric acid was added and the organic layer was separated. The aqueous layer was extracted with ether, the organic layers were combined, washed with water, dried, and the solvent was distilled off to remove 5,6-difluoroindene-2-carboxylic acid.
1.8 g (yield 86%) was obtained.
【0139】[第3ステップ]次に、得られた5,6-ジフ
ルオロインデン-2- カルボン酸1.8gを50mlのトルエンに
溶解し、酸化白金触媒0.5gを加え、60℃に加温し、常圧
で接触還元を行って、2時間で計算量の水素を付加させ
た。触媒を濾別後、溶媒を減圧留去し、得られた粗結晶
をメタノールで再結晶して、5,6-ジフルオロインダン-2
- カルボン酸を1.5g(収率85%)得た。[Third step] Next, 1.8 g of the obtained 5,6-difluoroindene-2-carboxylic acid was dissolved in 50 ml of toluene, 0.5 g of a platinum oxide catalyst was added, and the mixture was heated to 60 ° C. Catalytic reduction was performed at atmospheric pressure, and a calculated amount of hydrogen was added in 2 hours. After the catalyst was filtered off, the solvent was distilled off under reduced pressure, and the resulting crude crystals were recrystallized from methanol to give 5,6-difluoroindane-2.
-Obtained 1.5 g of carboxylic acid (yield 85%).
【0140】[第4ステップ]次に、冷却管付きの50ml
三ツ口フラスコに塩化チオニル10g と得られた5,6-ジフ
ルオロインダン-2- カルボン酸1.5g(7.6mmol) を仕込み
2時間還流させた。冷却後、過剰の塩化チオニルを留去
して、5,6-ジフルオロインダン-2- カルボン酸クロリド
を1.5g(収率90%)得た。[Fourth step] Next, 50 ml with a cooling tube
A three-necked flask was charged with 10 g of thionyl chloride and 1.5 g (7.6 mmol) of the obtained 5,6-difluoroindane-2-carboxylic acid, and the mixture was refluxed for 2 hours. After cooling, excess thionyl chloride was distilled off to obtain 1.5 g of 5,6-difluoroindane-2-carboxylic acid chloride (yield 90%).
【0141】[第5ステップ]次いで、冷却管付きの10
0ml 三ツ口フラスコに塩化メチレン50mlと得られた5,6-
ジフルオロインダン-2- カルボン酸クロリド0.7g(3.2mm
ol) およびトリエチルアミン0.4gを仕込み、0 ℃にて4-
n-プロピルフェノール0.5g(3.8mmol) の塩化メチレン溶
液を滴下した。滴下終了後、さらに室温で2時間撹拌
後、1N塩酸を加え、有機層を分離した。水層を塩化メチ
レンで抽出し、有機層を合わせて水洗、乾燥後、溶媒を
留去し、得られた固体をカラムクロマトグラフィーにて
精製して、2-(4-n- プロピルフェノキシカルボニル)-5,
6-ジフルオロインダンを1.0g(収率95%)得た。 n-C3H7-Ph-OOC-In(F)[Fifth Step] Next, 10 with a cooling pipe
Obtained 5,6-methylene chloride 50 ml in a 0 ml three-necked flask
0.7 g (3.2 mm) of difluoroindane-2-carboxylic acid chloride
ol) and 0.4 g of triethylamine were charged, and 4-
A methylene chloride solution of 0.5 g (3.8 mmol) of n-propylphenol was added dropwise. After completion of dropping, the mixture was further stirred at room temperature for 2 hours, 1N hydrochloric acid was added, and the organic layer was separated. The aqueous layer was extracted with methylene chloride, the organic layers were combined, washed with water, dried and the solvent was distilled off.The obtained solid was purified by column chromatography to give 2- (4-n-propylphenoxycarbonyl). -Five,
1.0 g (yield 95%) of 6-difluoroindane was obtained. nC 3 H 7 -Ph-OOC-In (F)
【0142】[0142]
【化27】 [Chemical 27]
【0143】本化合物の分析結果を以下に示す。 MS m/e 316(M+)The analysis results of this compound are shown below. MS m / e 316 (M + )
【0144】実施例9と同様にして、以下の化合物を得
ることができる。 n-C3H7-Cy-OOC-In(F) n-C3H7-Ch-OOC-In(F) n-C3H7O-Ph-OOC-In(F)The following compounds can be obtained in the same manner as in Example 9. nC 3 H 7 -Cy-OOC-In (F) nC 3 H 7 -Ch-OOC-In (F) nC 3 H 7 O-Ph-OOC-In (F)
【0145】実施例10 50mlの三ツ口フラスコに乾燥THF30mlと実施例9の第
3ステップにおいて得られた5,6-ジフルオロインダン-2
- カルボン酸0.7g(3.2mmol) を仕込み-78 ℃に冷却後、
ジイソブチルアルミニウムハイドライド(DIBAL−
H)のTHF溶液(1.0M)3.5ml(3.5mmol)を滴下した。滴
下後、-78 ℃で30分撹拌し、さらに室温にもどして4時
間撹拌し、1N塩酸を加え、ジエチルエーテルで抽出し、
水洗、乾燥後、溶媒を留去して、2-( ヒドロキシメチ
ル)-5,6-ジフルオロインダンを0.5g(収率92%)得た。 HOCH2-In(F)Example 10 30 ml of dry THF in a 50 ml three-necked flask and 5,6-difluoroindane-2 obtained in the third step of Example 9.
-Charge 0.7 g (3.2 mmol) of carboxylic acid, cool to -78 ° C,
Diisobutyl Aluminum Hydride (DIBAL-
A solution of H) in THF (1.0 M) (3.5 ml, 3.5 mmol) was added dropwise. After dropping, the mixture was stirred at -78 ° C for 30 minutes, further returned to room temperature and stirred for 4 hours, 1N hydrochloric acid was added, and the mixture was extracted with diethyl ether,
After washing with water and drying, the solvent was distilled off to obtain 0.5 g of 2- (hydroxymethyl) -5,6-difluoroindane (yield 92%). HOCH 2 -In (F)
【0146】次いで、得られた2-( ヒドロキシメチル)-
5,6-ジフルオロインダン 0.5g(2.9mmol)を無水の塩化メ
チレン30mlに溶かし、アルゴン気流下、室温で PPh3 1.
4g(5.3mmol) と CBr4 2.2g(6.6mmol) を加えた。30分撹
拌し炭酸水素ナトリウム水溶液を加えて洗浄後、有機層
を飽和食塩水で洗浄、乾燥、濃縮した。カラムクロマト
グラフィーで精製し、2-( ブロモメチル)-5,6-ジフルオ
ロインダンを0.5g(収率70%)得た。 BrCH2-In(F)Then, the obtained 2- (hydroxymethyl)-
0.5 g (2.9 mmol) of 5,6-difluoroindane was dissolved in 30 ml of anhydrous methylene chloride, and PPh 3 1.
4 g (5.3 mmol) and CBr 4 2.2 g (6.6 mmol) were added. After stirring for 30 minutes and adding an aqueous sodium hydrogen carbonate solution for washing, the organic layer was washed with saturated brine, dried and concentrated. Purification by column chromatography gave 0.5 g (yield 70%) of 2- (bromomethyl) -5,6-difluoroindane. BrCH 2 -In (F)
【0147】冷却管付きの50ml三ツ口フラスコに塩化メ
チレン30mlと得られた2-( ブロモメチル)-5,6-ジフルオ
ロインダン0.5g(2.0mmol) およびトリエチルアミン0.4g
を仕込み、0 ℃にて4-n-プロピルフェノール0.3g(2.2mm
ol) の塩化メチレン溶液を滴下した。滴下終了後、4時
間加熱還流し、冷却後、1N塩酸を加え、有機層を分離し
た。水層を塩化メチレンで抽出し、有機層を合わせて水
洗、乾燥後、溶媒を留去し、得られた固体をカラムクロ
マトグラフィーにて精製して、2-(4- メチルフェノキシ
メチル)-5,6- ジフルオロインダンを0.5g(収率88%)
得た。 CH3-Ph-OCH2-In(F)In a 50 ml three-necked flask equipped with a cooling tube, 30 ml of methylene chloride and 0.5 g (2.0 mmol) of 2- (bromomethyl) -5,6-difluoroindane obtained and 0.4 g of triethylamine were added.
, 4-n-propylphenol 0.3g (2.2mm
ol) in methylene chloride was added dropwise. After completion of the dropwise addition, the mixture was heated under reflux for 4 hours, cooled, 1N hydrochloric acid was added, and the organic layer was separated. The aqueous layer was extracted with methylene chloride, the organic layers were combined, washed with water, dried and the solvent was distilled off. The obtained solid was purified by column chromatography to give 2- (4-methylphenoxymethyl) -5. 0.5g of 6,6-difluoroindane (88% yield)
Obtained. CH 3 -Ph-OCH 2 -In (F)
【0148】[0148]
【化28】 [Chemical 28]
【0149】本化合物の分析結果を以下に示す。 MS m/e 274(M+)The analysis results of this compound are shown below. MS m / e 274 (M + )
【0150】実施例10と同様にして、以下の化合物を
得ることができる。 n-C3H7-Ph-OCH2-In(F) n-C3H7-Cy-OCH2-In(F) n-C3H7-Ch-OCH2-In(F) n-C3H7O-Ph-OCH2-In(F)The following compounds can be obtained in the same manner as in Example 10. nC 3 H 7 -Ph-OCH 2 -In (F) nC 3 H 7 -Cy-OCH 2 -In (F) nC 3 H 7 -Ch-OCH 2 -In (F) nC 3 H 7 O-Ph- OCH 2 -In (F)
【0151】実施例11 アルゴン雰囲気下、還流管付きの 100ml三ツ口フラスコ
にマグネシウム0.09g(3.5mmol)および乾燥THF10mlを
入れた。次いで、1-ブロモプロパンを数滴加え、さらに
4-n-プロピルベンジルブロミド0.7g(3.2mmol) を発熱が
続く速度で滴下した。滴下終了後、さらに 1時間還流を
続けた後、室温まで放冷した。Example 11 0.09 g (3.5 mmol) of magnesium and 10 ml of dry THF were placed in a 100 ml three-necked flask equipped with a reflux tube under an argon atmosphere. Then add a few drops of 1-bromopropane and
0.7 g (3.2 mmol) of 4-n-propylbenzyl bromide was added dropwise at a rate at which exotherm continued. After the dropwise addition was completed, the mixture was refluxed for another hour and then allowed to cool to room temperature.
【0152】次いで、ZnCl2 を0.5g(3.8mmol) 加え、室
温で4時間撹拌後、さらにPd(PPh3)4 を0.1gおよび実施
例9の第4ステップにおいて得られた5,6-ジフルオロイ
ンダン-2- カルボン酸クロリド0.7g(3.2mmol) を加え、
室温で12時間撹拌後、1N塩酸を加え、有機層を分離し
た。水層を塩化メチレンで抽出し、有機層を合わせて水
洗、乾燥後、溶媒を留去し、得られた固体をカラムクロ
マトグラフィーにて精製して、2-(4-n- プロピルベンジ
ルカルボニル)-5,6-ジフルオロインダンを0.6g(収率60
%)得た。Next, 0.5 g (3.8 mmol) of ZnCl 2 was added, and after stirring at room temperature for 4 hours, 0.1 g of Pd (PPh 3 ) 4 and 5,6-difluoro obtained in the fourth step of Example 9 were further added. 0.7 g (3.2 mmol) of indan-2-carboxylic acid chloride was added,
After stirring at room temperature for 12 hours, 1N hydrochloric acid was added and the organic layer was separated. The aqueous layer was extracted with methylene chloride, the organic layers were combined, washed with water and dried, the solvent was evaporated, and the obtained solid was purified by column chromatography to give 2- (4-n-propylbenzylcarbonyl). -0.6 g of -5,6-difluoroindane (yield 60
%)Obtained.
【0153】50mlの三ツ口フラスコに乾燥THF30mlと
得られた2-(4-n- プロピルベンジルカルボニル)-5,6-ジ
フルオロインダン0.6g(1.9mmol) を仕込み-78 ℃に冷却
後、ジイソブチルアルミニウムハイドライド(DIBA
L−H)のTHF溶液(1.0M)2.0ml(2.0mmol)を滴下し
た。滴下後、-78 ℃で30分撹拌し、さらに室温にもどし
て4時間撹拌し、1N塩酸を加え、ジエチルエーテルで抽
出し、水洗、乾燥後、溶媒を留去して、2-(4-n- プロピ
ルベンジルヒドロキシメチル)-5,6-ジフルオロインダン
を0.5g(収率90%)得た。A 50 ml three-necked flask was charged with 30 ml of dry THF and 0.6 g (1.9 mmol) of 2- (4-n-propylbenzylcarbonyl) -5,6-difluoroindane obtained, and after cooling to -78 ° C, diisobutylaluminum hydride was added. (DIBA
L-H) THF solution (1.0 M) 2.0 ml (2.0 mmol) was added dropwise. After dropping, the mixture was stirred at -78 ° C for 30 minutes, further returned to room temperature and stirred for 4 hours, 1N hydrochloric acid was added, extracted with diethyl ether, washed with water, dried, and the solvent was distilled off to give 2- (4- 0.5 g (yield 90%) of n-propylbenzylhydroxymethyl) -5,6-difluoroindane was obtained.
【0154】次いで、得られた2-(4-n- プロピルベンジ
ルヒドロキシメチル)-5,6-ジフルオロインダン0.5g(1.6
mmol) をトルエン10mlに溶解し、p-トルエンスルホン酸
を0.5g加え、加熱還流した。冷却後、水洗、乾燥後、溶
媒を留去し、得られた固体をカラムクロマトグラフィー
にて精製して、2-[2-(4-n- プロピルフェニル) エテニ
ル]-5,6- ジフルオロインダンを0.4g(収率80%)得
た。 n-C3H7-Ph-CH=CH-In(F)Then, 0.5 g (1.6 g of obtained 2- (4-n-propylbenzylhydroxymethyl) -5,6-difluoroindane) was obtained.
mmol) was dissolved in 10 ml of toluene, 0.5 g of p-toluenesulfonic acid was added, and the mixture was heated under reflux. After cooling, washing with water and drying, the solvent was distilled off, and the obtained solid was purified by column chromatography to give 2- [2- (4-n-propylphenyl) ethenyl] -5,6-difluoroindane. 0.4 g (yield 80%) was obtained. nC 3 H 7 -Ph-CH = CH-In (F)
【化29】 [Chemical 29]
【0155】本化合物の分析結果を以下に示す。 MS m/e 298(M+)The analysis results of this compound are shown below. MS m / e 298 (M + )
【0156】実施例11と同様にして、以下の化合物を
得ることができる。 n-C3H7-Cy-CH=CH-In(F) n-C3H7-Ch-CH=CH-In(F) n-C3H7O-Ph-CH=CH-In(F)The following compounds can be obtained in the same manner as in Example 11. nC 3 H 7 -Cy-CH = CH-In (F) nC 3 H 7 -Ch-CH = CH-In (F) nC 3 H 7 O-Ph-CH = CH-In (F)
【0157】実施例12 50mlの三ツ口フラスコに塩化メチレン20mlと実施例11
で得られた2-[2-(4-n- プロピルフェニル) エテニル]
-5,6- ジフルオロインダン0.3g(1.0mmol) を仕込み、室
温で臭素0.16g(1.0mmol)を加え、1時間撹拌した。反応
液にチオ硫酸ナトリウム水溶液を加え、塩化メチレンで
抽出した。水洗、乾燥後、溶媒を留去して2-[1,2-ジブ
ロモ-2-(4-n-プロピルフェニル) エチル]-5,6- ジフル
オロインダンを0.44g (収率96%)得た。Example 12 Example 11 with 20 ml of methylene chloride in a 50 ml three-necked flask.
2- [2- (4-n-propylphenyl) ethenyl] obtained in
0.3 g (1.0 mmol) of -5,6-difluoroindane was charged, 0.16 g (1.0 mmol) of bromine was added at room temperature, and the mixture was stirred for 1 hour. An aqueous sodium thiosulfate solution was added to the reaction solution, and the mixture was extracted with methylene chloride. After washing with water and drying, the solvent was distilled off to obtain 0.44 g (yield 96%) of 2- [1,2-dibromo-2- (4-n-propylphenyl) ethyl] -5,6-difluoroindane. .
【0158】次いで、得られた2-[1,2-ジブロモ-2-(4-
n-プロピルフェニル) エチル]-5,6- ジフルオロインダ
ン0.44g を無水THF20mlに溶解し、カリウム-t- ブト
キシド0.22g(2mmol)を加え、40℃にて2時間撹拌した。
冷却後、水を加え、塩化メチレンで抽出した。水洗、乾
燥後、溶媒を留去し、得られた固体をカラムクロマトグ
ラフィーにて精製して、2-[2-(4-n- プロピルフェニ
ル) エチニル]-5,6- ジフルオロインダンを0.24g (収
率85%)得た。 n-C3H7-Ph-C ≡C-In(F)Then, the obtained 2- [1,2-dibromo-2- (4-
0.44 g of (n-propylphenyl) ethyl] -5,6-difluoroindane was dissolved in 20 ml of anhydrous THF, 0.22 g (2 mmol) of potassium-t-butoxide was added, and the mixture was stirred at 40 ° C. for 2 hours.
After cooling, water was added and the mixture was extracted with methylene chloride. After washing with water and drying, the solvent was distilled off, and the obtained solid was purified by column chromatography to give 0.24 g of 2- [2- (4-n-propylphenyl) ethynyl] -5,6-difluoroindane. (Yield 85%) was obtained. nC 3 H 7 -Ph-C ≡ C-In (F)
【0159】[0159]
【化30】 [Chemical 30]
【0160】本化合物の分析結果を以下に示す。 MS m/e 296(M+)The analysis results of this compound are shown below. MS m / e 296 (M + )
【0161】実施例12と同様にして、以下の化合物を
得ることができる。 n-C3H7-Cy-C ≡C-In(F) n-C3H7-Ch-C ≡C-In(F) n-C3H7O-Ph-C≡C-In(F)The following compounds can be obtained in the same manner as in Example 12. nC 3 H 7 -Cy-C ≡ C-In (F) nC 3 H 7 -Ch-C ≡ C-In (F) nC 3 H 7 O-Ph-C ≡ C-In (F)
【0162】実施例13 ガス吹き込み管およびドライアイスコンデンサ付の50ml
三ツ口フラスコに−78℃にてI21.3g(5mmol) を、CFCl3
20ml中に懸濁させ、そこにN2で希釈した10%F2ガスをI2
が赤色から茶色になるまで吹き込み、フッ化ヨウ素(IF)
を製造した。Example 13 50 ml with gas blowing tube and dry ice condenser
I 2 1.3 g (5 mmol) was added to a three- necked flask at -78 ° C with CFCl 3
It was suspended in 20 ml, and 10% F 2 gas diluted with N 2 was added to I 2
Blow from red to brown, iodine fluoride (IF)
Was manufactured.
【0163】実施例12で得られた2-[2-(4-n- プロピ
ルフェニル) エチニル]-5,6- ジフルオロインダン0.15
g(0.5mmol)を20mlのCHCl3 に溶解し、−78℃に冷却す
る。ここへ撹拌しながら、予め調製した10mmolのIFを添
加した。 5分後、反応液を50mlの 5%チオ硫酸ナトリウ
ム水溶液に投入した。有機層を分液し、中性になるまで
水洗後、MgSO4 で乾燥した。濾過後、溶媒を留去て、2-
[2-(4-n- プロピルフェニル)-1,1,2,2-テトラフルオロ
エチル]-5,6- ジフルオロインダンを0.13g (収率70
%)得た。 n-C3H7-Ph-CF2CF2-In(F)2- [2- (4-n-propylphenyl) ethynyl] -5,6-difluoroindane 0.15 obtained in Example 12
g (0.5 mmol) is dissolved in 20 ml CHCl 3 and cooled to −78 ° C. While stirring, 10 mmol of IF prepared in advance was added thereto. After 5 minutes, the reaction solution was poured into 50 ml of a 5% sodium thiosulfate aqueous solution. The organic layer was separated, washed with water until neutral, and dried over MgSO 4 . After filtration, the solvent is distilled off to give 2-
[2- (4-n-Propylphenyl) -1,1,2,2-tetrafluoroethyl] -5,6-difluoroindane 0.13 g (yield 70
%)Obtained. nC 3 H 7 -Ph-CF 2 CF 2 -In (F)
【0164】[0164]
【化31】 [Chemical 31]
【0165】本化合物の分析結果を以下に示す。 MS m/e 372(M+)The analysis results of this compound are shown below. MS m / e 372 (M + )
【0166】実施例13と同様にして、以下の化合物を
得ることができる。 n-C3H7-Cy-CF2CF2-In(F) n-C3H7-Ch-CF2CF2-In(F) n-C3H7O-Ph-CF2CF2-In(F)The following compounds can be obtained in the same manner as in Example 13. nC 3 H 7 -Cy-CF 2 CF 2 -In (F) nC 3 H 7 -Ch-CF 2 CF 2 -In (F) nC 3 H 7 O-Ph-CF 2 CF 2 -In (F)
【0167】実施例14 [第1ステップ]冷却管およびガス吹き込み管付きの50
mlの三ツ口フラスコにTHFを30ml入れ、−100 ℃に冷
却した。ここにクロロトリフルオロエチレンを1.2g(10.
3mmol)吹き込んだ。次いで、n-ブチルリチウムのn-ヘキ
サン溶液(1.65M) 6.3ml(10.4mol)を徐々に滴下し、30分
撹拌後、さらにクロロトリメチルシラン1.2g(11.1mol)
を滴下した。Example 14 [First Step] 50 with cooling pipe and gas blowing pipe
30 ml of THF was placed in a three-necked ml flask and cooled to -100 ° C. Chlorotrifluoroethylene 1.2g (10.
It was blown in (3 mmol). Then, n-hexane solution of n-butyllithium (1.65M) 6.3 ml (10.4 mol) was gradually added dropwise, and after stirring for 30 minutes, 1.2 g (11.1 mol) of chlorotrimethylsilane was further added.
Was dripped.
【0168】滴下後、さらに 1時間撹拌後、2-クロロ-
5,6- ジフルオロインダン2.0g(10.5mmol)とリチウム0.1
5g(21mmol) によって別途合成した2-リチオ−5,6-ジフ
ルオロインダンのエーテル溶液を−100 ℃にて滴下し
た。さらに 0℃にて 2時間撹拌後、希塩酸水溶液を加
え、有機層を分離した。水層を塩化メチレンで抽出し、
有機層を合わせて乾燥後、溶媒を留去し、(Z)-1,2-ジフ
ルオロ-1-(5,6-ジフルオロインダン-2- イル)-2-トリメ
チルシリルエチレンを2.1g(収率70%)得た。 (CH3)3Si-CF=CF-In(F)After the dropping, the mixture was further stirred for 1 hour, and then 2-chloro-
5,6-difluoroindane 2.0 g (10.5 mmol) and lithium 0.1
An ether solution of 2-lithio-5,6-difluoroindane separately synthesized with 5 g (21 mmol) was added dropwise at -100 ° C. After stirring at 0 ° C. for 2 hours, a dilute hydrochloric acid aqueous solution was added, and the organic layer was separated. Extract the aqueous layer with methylene chloride,
After the organic layers were combined and dried, the solvent was distilled off, and 2.1 g of (Z) -1,2-difluoro-1- (5,6-difluoroindan-2-yl) -2-trimethylsilylethylene (yield 70 %)Obtained. (CH 3 ) 3 Si-CF = CF-In (F)
【0169】[第2ステップ]次に、得られた(Z)-1,2-
ジフルオロ-1-(5,6-ジフルオロインダン-2- イル)-2-ト
リメチルシリルエチレン2.1g(7.2mmol) を30mlのアセト
ニトリルに溶解し、フッ化カリウム0.9g(16mmol)および
水0.4g(22mmol)を加え、70℃にて 1時間反応させた。冷
却後、水50mlを注ぎ、塩化メチレンで抽出し、有機層を
飽和食塩水で洗浄し、CaCl2 で乾燥した。濾過後、溶媒
および低沸物を留去し、さらに減圧蒸留して(E)-1,2-ジ
フルオロ-1-(5,6-ジフルオロインダン-2- イル) エチレ
ンを1.2g(収率80%)得た。 CFH=CF-In(F)[Second Step] Next, the obtained (Z) -1,2-
2.1 g (7.2 mmol) of difluoro-1- (5,6-difluoroindan-2-yl) -2-trimethylsilylethylene was dissolved in 30 ml of acetonitrile, 0.9 g (16 mmol) of potassium fluoride and 0.4 g (22 mmol) of water. Was added and reacted at 70 ° C for 1 hour. After cooling, 50 ml of water was poured, the mixture was extracted with methylene chloride, the organic layer was washed with saturated saline and dried over CaCl 2 . After filtration, the solvent and low-boiling substances were distilled off, and the residue was distilled under reduced pressure to obtain 1.2 g of (E) -1,2-difluoro-1- (5,6-difluoroindan-2-yl) ethylene (yield 80 %)Obtained. CFH = CF-In (F)
【0170】[第3ステップ]次いで、得られた(E)-1,
2-ジフルオロ-1-(5,6-ジフルオロインダン-2- イル)エ
チレンを1.2g(5.8mmol) を乾燥THF30mlに溶解し、−
78℃に冷却した。ここn-ブチルリチウムのn-ヘキサン溶
液(1.61M) 4.0ml(6.4mmol)を徐々に滴下し、30分撹拌
後、ZnCl2 0.87g(6.4mmol)を加え、室温まで昇温後、1
時間撹拌した。次いで、Pd(PPh3)4 0.1gおよび1-ヨード
−4-n-プロピルベンゼン1.4g(5.8mmol) を加え、3時間
加熱還流した。冷却後、希塩酸を加え、塩化メチレンで
抽出した。水洗、乾燥後、溶媒を留去し、得られた固体
をカラムクロマトグラフィーにて精製して、2-[1,2-ジ
フルオロ-2-(4-n-プロピルフェニル) エチル]-5,6- ジ
フルオロインダンを0.24g (収率70%)得た。 n-C3H7-Ph-CF=CF-In(F)[Third Step] Then, the obtained (E) -1,
1.2 g (5.8 mmol) of 2-difluoro-1- (5,6-difluoroindan-2-yl) ethylene was dissolved in 30 ml of dry THF,
Cooled to 78 ° C. 4.0 ml (6.4 mmol) of n-hexane solution of n-butyllithium (1.61M) was slowly added dropwise thereto, and after stirring for 30 minutes, 0.87 g (6.4 mmol) of ZnCl 2 was added, and after warming to room temperature, 1
Stir for hours. Next, 0.1 g of Pd (PPh 3 ) 4 and 1.4 g (5.8 mmol) of 1-iodo-4-n-propylbenzene were added, and the mixture was heated under reflux for 3 hours. After cooling, diluted hydrochloric acid was added and the mixture was extracted with methylene chloride. After washing with water and drying, the solvent was distilled off, and the obtained solid was purified by column chromatography to give 2- [1,2-difluoro-2- (4-n-propylphenyl) ethyl] -5,6. -0.24 g (yield 70%) of difluoroindane was obtained. nC 3 H 7 -Ph-CF = CF-In (F)
【0171】[0171]
【化32】 [Chemical 32]
【0172】本化合物の分析結果を以下に示す。 MS m/e 334(M+)The analysis results of this compound are shown below. MS m / e 334 (M + )
【0173】実施例14と同様にして、以下の化合物を
得ることができる。 n-C3H7-Cy-CF=CF-In(F) n-C3H7-Ch-CF=CF-In(F) n-C3H7O-Ph-CF=CF-In(F)The following compounds can be obtained in the same manner as in Example 14. nC 3 H 7 -Cy-CF = CF-In (F) nC 3 H 7 -Ch-CF = CF-In (F) nC 3 H 7 O-Ph-CF = CF-In (F)
【0174】実施例15 アルゴン雰囲気下、還流管付きの 100ml三ツ口フラスコ
にマグネシウム0.17g(7.0mmol)および乾燥THF10mlを
入れた。次いで、1-ブロモプロパンを数滴加え、さらに
1,4-ジブロモベンゼン1.6g(6.9mmol) を発熱が続く速度
で滴下した。滴下終了後、さらに 1時間還流を続けた
後、室温まで放冷した。Example 15 Under an argon atmosphere, 0.17 g (7.0 mmol) of magnesium and 10 ml of dry THF were placed in a 100 ml three-necked flask equipped with a reflux tube. Then add a few drops of 1-bromopropane and
1.6 g (6.9 mmol) of 1,4-dibromobenzene was added dropwise at a rate at which heat generation continued. After the dropwise addition was completed, the mixture was refluxed for another hour and then allowed to cool to room temperature.
【0175】次に、別途調製した5,6-ジメチル-2- イン
ダノン1.0g(6.0mmol) のエーテル溶液の中に上記溶液を
10℃以下にて滴下した。さらに、室温まで昇温し、4時
間撹拌後、1N塩酸水溶液を加え、有機層を分離した。水
層をエーテルで抽出し、有機層を合わせて水洗、乾燥
後、溶媒を留去し、2-(4-ブロモフェニル)-5,6- ジフ
ルオロインダン-2- オールを1.5g( 収率75%)得た。以
下、実施例1と同様に反応を行い、2-(4-ブロモフェニ
ル)-5,6- ジフルオロインダンを1.1g( 収率80%)得
た。Next, the above solution was added to a separately prepared ether solution of 5,6-dimethyl-2-indanone (1.0 g, 6.0 mmol).
It was added dropwise at 10 ° C or lower. Furthermore, the temperature was raised to room temperature, and after stirring for 4 hours, a 1N hydrochloric acid aqueous solution was added, and the organic layer was separated. The aqueous layer was extracted with ether, the organic layers were combined, washed with water, dried, and the solvent was distilled off to give 1.5 g of 2- (4-bromophenyl) -5,6-difluoroindan-2-ol (yield 75 %)Obtained. Then, the same reaction as in Example 1 was performed to obtain 1.1 g (yield 80%) of 2- (4-bromophenyl) -5,6-difluoroindane.
【0176】次いで、アルゴン雰囲気下、還流管付きの
100ml三ツ口フラスコにマグネシウム0.1g(4.0mmol) お
よび乾燥THF10mlを入れた。次いで、1-ブロモプロパ
ンを数滴加え、さらにアリルブロミド0.48g(4.0mmol)を
発熱が続く速度で滴下した。滴下終了後、さらに 1時間
還流を続けた後、室温まで放冷した。Then, under an argon atmosphere,
A 100 ml three-necked flask was charged with 0.1 g (4.0 mmol) of magnesium and 10 ml of dry THF. Next, a few drops of 1-bromopropane were added, and 0.48 g (4.0 mmol) of allyl bromide was further added dropwise at a rate at which heat generation continued. After the dropwise addition was completed, the mixture was refluxed for another hour and then allowed to cool to room temperature.
【0177】別途、アルゴン雰囲気下、還流管付き 100
ml三ツ口フラスコ中に先に得られた2-(4-ブロモフェニ
ル)-5,6- ジフルオロインダンを1.1g(3.6mmol) および
1,3-ビス(ジフェニルホスフィノ)プロパンジクロロニ
ッケル[NiCl2(dppp)]0.1g を含む乾燥THF20mlを入
れ、この中に上記溶液を滴下漏斗を用いて滴下した。Separately, in an argon atmosphere, with a reflux tube 100
1.1 g (3.6 mmol) of 2- (4-bromophenyl) -5,6-difluoroindane obtained above in a 3-ml three-necked flask and
20 ml of dry THF containing 0.1 g of 1,3-bis (diphenylphosphino) propanedichloronickel [NiCl 2 (dppp)] was placed, and the above solution was added dropwise thereto using a dropping funnel.
【0178】滴下後さらに室温にて24時間撹拌した後、
水50mlを加えた。さらに20%塩酸20mlを加えて有機層を
分離し、水洗、乾燥後、溶媒を留去した。得られた粗生
成物をシリカゲルカラムクロマトグラフィーにて精製し
て、4-アリルフェニル-5,6-ジフルオロインダンを0.49g
( 収率50%)得た。 CH2=CHCH2-Ph-In(F)After the dropping, the mixture was further stirred at room temperature for 24 hours,
50 ml of water was added. Further, 20 ml of 20% hydrochloric acid was added to separate the organic layer, which was washed with water and dried, and then the solvent was distilled off. The obtained crude product was purified by silica gel column chromatography to give 4-allylphenyl-5,6-difluoroindane (0.49 g).
(Yield 50%) was obtained. CH 2 = CHCH 2 -Ph-In (F)
【0179】[0179]
【化33】 [Chemical 33]
【0180】本化合物の分析結果を以下に示す。 MS m/e 270(M+)The analysis results of this compound are shown below. MS m / e 270 (M + )
【0181】実施例15と同様にして、以下の化合物を
得ることができる。 CH2=CHCH2-Cy-In(F) CH2=CHCH2-Ch-In(F) n-C3H7-Ph-CH=CH-Ph-In(F) n-C3H7-Ph-C ≡CH-Ph-In(F)The following compounds can be obtained in the same manner as in Example 15. CH 2 = CHCH 2 -Cy-In (F) CH 2 = CHCH 2 -Ch-In (F) nC 3 H 7 -Ph-CH = CH-Ph-In (F) nC 3 H 7 -Ph-C ≡ CH-Ph-In (F)
【0182】実施例16 メルク社製液晶組成物「ZLI-1565」80wt%に、本発明の
実施例1の化合物を20wt%加えて液晶組成物とし、偏光
板付きの液晶セルに封入して、STN型液晶表示素子を
作成した。Example 16 20 wt% of the compound of Example 1 of the present invention was added to 80 wt% of the liquid crystal composition "ZLI-1565" manufactured by Merck Ltd. to prepare a liquid crystal composition, which was sealed in a liquid crystal cell with a polarizing plate. An STN type liquid crystal display device was created.
【0183】比較例1 比較例として、メルク社製液晶組成物「ZLI-1565」のみ
の液晶組成物を作製し、偏光板付きの液晶セルに封入し
て、STN型液晶表示素子を作成した。Comparative Example 1 As a comparative example, a liquid crystal composition of only the liquid crystal composition “ZLI-1565” manufactured by Merck & Co., Inc. was prepared and enclosed in a liquid crystal cell with a polarizing plate to prepare an STN type liquid crystal display device.
【0184】これらの実施例16および比較例1の液晶
表示素子の素子の表示特性はほぼ同程度であったが、実
施例16の液晶表示素子は比較例1の液晶表示素子に比
べて低電圧駆動が実現できた。The display characteristics of the liquid crystal display elements of Example 16 and Comparative Example 1 were substantially the same, but the liquid crystal display element of Example 16 had a lower voltage than the liquid crystal display element of Comparative Example 1. Drive was realized.
【0185】次いで、実施例16の液晶表示素子を紫外
線カーボンアークランプで 200時間照射した。照射後、
各素子内の液晶組成物を分析した。その結果、実施例1
6の液晶組成物では、ほとんど新たな化合物の生成は認
められなかった。Then, the liquid crystal display device of Example 16 was irradiated with an ultraviolet carbon arc lamp for 200 hours. After irradiation,
The liquid crystal composition in each device was analyzed. As a result, Example 1
In the liquid crystal composition of No. 6, almost no new compound was formed.
【0186】[0186]
【発明の効果】本発明の下記一般式(1) で表される化合
物は、誘電率異方性が大きく、電荷保持率が高く、液晶
組成物として用いることにより、少量の添加でも応答速
度が向上するものであり、低電圧駆動、高デューティ駆
動、広温度域動作等が可能になる。 R-(A1)m-Y1-(A2)n-Y2-In(F) (1)The compound represented by the following general formula (1) of the present invention has a large dielectric anisotropy and a high charge retention, and when used as a liquid crystal composition, the response speed is small even when added in a small amount. As a result, low voltage driving, high duty driving, wide temperature range operation, and the like are possible. R- (A 1 ) m -Y 1- (A 2 ) n -Y 2 -In (F) (1)
【0187】また、紫外線等に対する耐久性も高く、そ
の高誘電率異方性の特徴を充分活かすことができる。Further, it is highly durable against ultraviolet rays and the like, and the feature of its high dielectric anisotropy can be fully utilized.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 FI 技術表示箇所 C07C 69/75 C 9279−4H 69/753 Z 9279−4H D 9279−4H 69/757 C 9279−4H 69/76 Z 9279−4H A 9279−4H 69/773 9279−4H 69/86 9279−4H 69/92 9279−4H C07D 239/26 8615−4C C09K 19/32 9279−4H 19/34 9279−4H // C07C 57/58 8930−4H 57/72 8930−4H (72)発明者 高 英昌 神奈川県横浜市神奈川区羽沢町松原1160番 地 エイ・ジー・テクノロジー株式会社内─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Internal reference number FI Technical display location C07C 69/75 C 9279-4H 69/753 Z 9279-4H D 9279-4H 69/757 C 9279- 4H 69/76 Z 9279-4H A 9279-4H 69/773 9279-4H 69/86 9279-4H 69/92 9279-4H C07D 239/26 8615-4C C09K 19/32 9279-4H 19/34 9279-4H // C07C 57/58 8930-4H 57/72 8930-4H (72) Inventor Hidemasa Taka 1160 Matsubara, Hazawa-machi, Kanagawa-ku, Yokohama, Kanagawa Prefecture A-G Technology Co., Ltd.
Claims (4)
ン環誘導体化合物。 R-(A1)m-Y1-(A2)n-Y2-In(F) (1) ただし、一般式(1) 中、A1、A2、Y1、Y2、R 、m 、n は
下記のものを示す。A1、A2は相互に独立してトランス-
1,4- シクロヘキシレン基、1-シクロヘキセン−1,4-イ
レン基および1,4-フェニレン基から選ばれる環基であ
り、これらの環基は夫々非置換であるかあるいは置換基
として1個以上のハロゲン原子、シアノ基を有し、これ
らの環基中環を構成する1個以上の=CH-基は窒素原子に
置換されていてもよく、また、環を構成する1個以上の
-CH2- 基は酸素原子もしくは硫黄原子に置換されていて
もよい。Y1、Y2は相互に独立して-COO- 、 -OCO-、-C≡
C-、-CH2CH2-、-CH=CH- 、-OCH2-、-CH2O-、-CF2CF2-、
-CF=CF- または単結合を示す。R は炭素数 1〜10のアル
キル基、ハロゲン原子あるいはシアノ基を示し、アルキ
ル基の場合には、このアルキル基中の炭素−炭素結合間
あるいはこのアルキル基と環基との間の炭素−炭素結合
間に酸素原子、カルボニルオキシ基、あるいはオキシカ
ルボニル基が挿入されてもよく、また、そのアルキル基
中の炭素−炭素結合の一部が三重結合あるいは二重結合
に置換されていてもよく、また、そのアルキル基内の1
個の-CH2- 基がカルボニル基に置換されていてもよく、
また、そのアルキル基中の水素原子の一部もしくはすべ
てがフッ素原子に置換されていてもよい。m 、n は相互
に独立して 0または 1を示す。また、-In(F)は、5,6-ジ
フルオロインダン-2- イル基を示す。1. A fluorine-containing indane ring derivative compound represented by the following general formula (1). R- (A 1 ) m -Y 1- (A 2 ) n -Y 2 -In (F) (1) However, in the general formula (1), A 1 , A 2 , Y 1 , Y 2 , R 2 , m and n are as follows. A 1 and A 2 are transformers independent of each other.
A cyclic group selected from a 1,4-cyclohexylene group, a 1-cyclohexene-1,4-ylene group and a 1,4-phenylene group, and each of these cyclic groups is unsubstituted or has one substituent. One or more = CH- groups which have the above halogen atoms and cyano groups and which form a ring in these ring groups may be substituted with a nitrogen atom, and one or more
The —CH 2 — group may be substituted with an oxygen atom or a sulfur atom. Y 1 and Y 2 are independently of each other -COO-, -OCO-, -C≡
C-, -CH 2 CH 2- , -CH = CH-, -OCH 2- , -CH 2 O-, -CF 2 CF 2- ,
-CF = CF- or indicates a single bond. R represents an alkyl group having 1 to 10 carbon atoms, a halogen atom or a cyano group. An oxygen atom, a carbonyloxy group, or an oxycarbonyl group may be inserted between the bonds, and part of the carbon-carbon bond in the alkyl group may be replaced with a triple bond or a double bond, In addition, 1 in the alkyl group
-CH 2 -groups may be substituted with a carbonyl group,
Further, some or all of the hydrogen atoms in the alkyl group may be replaced with fluorine atoms. m and n independently represent 0 or 1. In addition, -In (F) represents a 5,6-difluoroindan-2-yl group.
R については、一般式(1) のものと同じものを示す)で
表される請求項1の含フッ素インダン環誘導体化合物。 R-In(F) (2)2. The following general formula (2) (wherein general formula (2):
The fluorine-containing indane ring derivative compound according to claim 1, represented by the general formula (1). R-In (F) (2)
ン環誘導体化合物を含有する液晶組成物。3. A liquid crystal composition containing the fluorine-containing indane ring derivative compound according to claim 1 or 2.
ン環誘導体化合物を電極付基板間に挟持してなる液晶電
気光学素子。4. A liquid crystal electro-optical element comprising the fluorine-containing indane ring derivative compound according to claim 1 or 2 sandwiched between substrates with electrodes.
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